U.S. patent application number 14/803994 was filed with the patent office on 2015-11-12 for flame-retardant urethane resin composition.
This patent application is currently assigned to Sekisui Chemical Co., Ltd.. The applicant listed for this patent is Sekisui Chemical Co., Ltd.. Invention is credited to Taichi Makida, Yousuke Okada, Takehiko Ushimi, Toshitaka Yoshitake.
Application Number | 20150322195 14/803994 |
Document ID | / |
Family ID | 51209488 |
Filed Date | 2015-11-12 |
United States Patent
Application |
20150322195 |
Kind Code |
A1 |
Makida; Taichi ; et
al. |
November 12, 2015 |
FLAME-RETARDANT URETHANE RESIN COMPOSITION
Abstract
A flame-retardant urethane resin composition comprises a
polyisocyanate compound, a polyol compound, a trimerization
catalyst, a foaming agent, a foam stabilizer, and an additive, in
which the trimerization catalyst is at least one selected from the
group consisting of a nitrogen-containing aromatic compound, a
carboxylic acid alkali metal salt, a tertiary ammonium salt, and a
quaternary ammonium salt, and the additive comprises red phosphorus
and at least one selected from the group consisting of a phosphoric
acid ester, a phosphate-containing flame retardant, a
bromine-containing flame retardant, a boron-containing flame
retardant, an antimony-containing flame retardant, and a metal
hydroxide.
Inventors: |
Makida; Taichi; (Saitama,
JP) ; Yoshitake; Toshitaka; (Saitama, JP) ;
Okada; Yousuke; (Saitama, JP) ; Ushimi; Takehiko;
(Saitama, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sekisui Chemical Co., Ltd. |
Osaka |
|
JP |
|
|
Assignee: |
Sekisui Chemical Co., Ltd.
Osaka
JP
|
Family ID: |
51209488 |
Appl. No.: |
14/803994 |
Filed: |
July 20, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2014/000251 |
Jan 20, 2014 |
|
|
|
14803994 |
|
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Current U.S.
Class: |
521/103 ;
521/106; 521/107; 521/123 |
Current CPC
Class: |
C08K 5/521 20130101;
C08G 18/225 20130101; C08G 18/06 20130101; C08J 9/0038 20130101;
C08G 18/18 20130101; C08G 18/1875 20130101; C08K 3/38 20130101;
C08K 3/32 20130101; C08G 18/1808 20130101; C08K 3/02 20130101; C08G
18/7671 20130101; C08J 9/144 20130101; C08G 18/2027 20130101; C08G
2105/02 20130101; C08G 2101/00 20130101; C08G 18/092 20130101; C08J
9/0047 20130101; C08G 18/48 20130101; C08K 2003/387 20130101; C08K
3/22 20130101; C08K 2003/026 20130101; C08G 18/4208 20130101; C08J
2375/04 20130101; C08K 3/2279 20130101; C08G 2101/0025 20130101;
C08K 2003/2227 20130101; C08K 3/02 20130101; C08L 75/04 20130101;
C08K 3/38 20130101; C08L 75/04 20130101 |
International
Class: |
C08G 18/06 20060101
C08G018/06; C08K 3/22 20060101 C08K003/22; C08K 3/32 20060101
C08K003/32; C08K 3/38 20060101 C08K003/38; C08K 5/521 20060101
C08K005/521 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 20, 2013 |
JP |
2013-007956 |
Sep 27, 2013 |
JP |
2013-201596 |
Claims
1. A flame-retardant urethane resin composition comprising: a
polyisocyanate compound; a polyol compound; a trimerization
catalyst; a foaming agent; a foam stabilizer; and an additive,
wherein the trimerization catalyst is at least one selected from
the group consisting of a nitrogen-containing aromatic compound, a
carboxylic acid alkali metal salt, a tertiary ammonium salt, and a
quaternary ammonium salt, and the additive comprises red phosphorus
and at least one selected from the group consisting of a phosphoric
acid ester, a phosphate-containing flame retardant, a
bromine-containing flame retardant, a boron-containing flame
retardant, an antimony-containing flame retardant, and a metal
hydroxide.
2. The flame-retardant urethane resin composition according to
claim 1, wherein the amount of the additive is within a range of
4.5 parts by weight to 70 parts by weight based on 100 parts by
weight of a urethane resin composed of the polyisocyanate compound
and the polyol compound, and the amount of the red phosphorus is
within a range of 3 parts by weight to 18 parts by weight based on
100 parts by weight of the urethane resin.
3. The flame-retardant urethane resin composition according to
claim 1, wherein the amount of the trimerization catalyst is within
a range of 0.6 parts by weight to 10 parts by weight based on 100
parts by weight of a urethane resin composed of the polyisocyanate
compound and the polyol compound.
4. The flame-retardant urethane resin composition according to
claim 1, wherein the amount of the foaming agent is within a range
of 0.1 parts by weight to 30 parts by weight based on 100 parts by
weight of a urethane resin composed of the polyisocyanate compound
and the polyol compound.
5. The flame-retardant urethane resin composition according to
claim 1, wherein the boron-containing flame retardant is at least
one selected from the group consisting of boron oxide, boric acid,
and a boric acid metal salt.
6. The flame-retardant urethane resin composition according to
claim 1, wherein an isocyanate index of the urethane resin is
within a range of 120 to 1,000.
7. The flame-retardant urethane resin composition according to
claim 2, wherein the amount of the trimerization catalyst is within
a range of 0.6 parts by weight to 10 parts by weight based on 100
parts by weight of the urethane resin.
8. The flame-retardant urethane resin composition according to
claim 7, wherein the amount of the foaming agent is within a range
of 0.1 parts by weight to 30 parts by weight based on 100 parts by
weight of the urethane resin.
9. The flame-retardant urethane resin composition according to
claim 8, wherein the boron-containing flame retardant is at least
one selected from the group consisting of boron oxide, boric acid,
and a boric acid metal salt.
10. The flame-retardant urethane resin composition according to
claim 9, wherein an isocyanate index of the urethane resin is
within a range of 120 to 1,000.
11. A method for producing a flame-retardant urethane resin
composition comprises: preparing an additive by mixing red
phosphorus and at least one selected from the group consisting of a
phosphoric acid ester, a phosphate-containing flame retardant, a
bromine-containing flame retardant, a boron-containing flame
retardant, an antimony-containing flame retardant, and a metal
hydroxide; preparing a mixture by mixing a polyol compound, a
trimerization catalyst, a forming agent, a foam stabilizer, and the
additive; and adding a polyisocyanate compound into the mixture,
wherein the trimerization catalyst is at least one selected from
the group consisting of a nitrogen-containing aromatic compound, a
carboxylic acid alkali metal salt, a tertiary ammonium salt, and a
quaternary ammonium salt.
12. The method for producing a flame-retardant urethane resin
composition according to claim 11, wherein the amount of the
additive is within a range of 4.5 parts by weight to 70 parts by
weight based on 100 parts by weight of a urethane resin composed of
the polyisocyanate compound and the polyol compound, and the amount
of the red phosphorus is within a range of 3 parts by weight to 18
parts by weight based on 100 parts by weight of the urethane
resin.
13. The method for producing a flame-retardant urethane resin
composition according to claim 11, wherein the amount of the
trimerization catalyst is within a range of 0.6 parts by weight to
10 parts by weight based on 100 parts by weight of a urethane resin
composed of the polyisocyanate compound and the polyol
compound.
14. The method for producing a flame-retardant urethane resin
composition according to claim 11, wherein the amount of the
foaming agent is within a range of 0.1 parts by weight to 30 parts
by weight based on 100 parts by weight of a urethane resin composed
of the polyisocyanate compound and the polyol compound.
15. The method for producing a flame-retardant urethane resin
composition according to claim 11, wherein the boron-containing
flame retardant is at least one selected from the group consisting
of boron oxide, boric acid, and a boric acid metal salt.
16. The method for producing a flame-retardant urethane resin
composition according to claim 11, wherein an isocyanate index of
the urethane resin is within a range of 120 to 1,000.
17. The method for producing a flame-retardant urethane resin
composition according to claim 12, wherein the amount of the
trimerization catalyst is within a range of 0.6 parts by weight to
10 parts by weight based on 100 parts by weight of the urethane
resin.
18. The method for producing a flame-retardant urethane resin
composition according to claim 17, wherein the amount of the
foaming agent is within a range of 0.1 parts by weight to 30 parts
by weight based on 100 parts by weight of the urethane resin.
19. The method for producing a flame-retardant urethane resin
composition according to claim 18, wherein the boron-containing
flame retardant is at least one selected from the group consisting
of boron oxide, boric acid, and a boric acid metal salt.
20. The method for producing a flame-retardant urethane resin
composition according to claim 19, wherein an isocyanate index of
the urethane resin is within a range of 120 to 1,000.
Description
BACKGROUND ART
[0001] Concrete has an advantage of maintaining strength over a
long period of time as a constructional material.
[0002] However, in a hot season such as summer, heat accumulates in
the concrete due to the outside air, direct sun rays, etc., and
thus the inside of a building is heated by the accumulated heat. In
addition, in winter, the concrete cools the inside of a
building.
[0003] Accordingly, insulation processing is usually performed on
the concrete. For example, an insulating layer is formed by
spraying hard polyurethane foam onto the surface of the concrete
such as a rebar-reinforced concrete used in multiple dwelling
houses such as apartments.
[0004] However, if the insulating layer is formed simply by
spraying the hard polyurethane foam, the hard, polyurethane foam
can burn easily in case of a fire in the building. Therefore,
polyurethane foams that have a self-extinguishable or flame
retardant property have been developed and are described, for
example, in Patent Literatures 1 to 12.
CITATION LIST
Patent Literature
[0005] [Patent Literature 1] JP-A-9-169863
[0006] [Patent Literature 2] JP-A-2010-053267
[0007] [Patent Literature 3] JP-A-2004-050495
[0008] [Patent Literature 4] JP-A-2002-338651
[0009] [Patent Literature 5] JP-A-3-152159
[0010] [Patent Literature 6] JP-A-61-261331
[0011] [Patent Literature 7] JP-A-2001-200027
[0012] [Patent Literature 8] JP-A-2010-7079
[0013] [Patent Literature 9] JP-A-2005-500417
[0014] [Patent Literature 10] JP-A-2009-187885
[0015] [Patent Literature 11] JP-A-2008-501063
[0016] [Patent Literature 12] JP-T-11-512125
SUMMARY OF THE INVENTION
[0017] One or more embodiments of the present disclosure provide a
flame-retardant urethane resin composition capable of forming foam
that can be handled easily, has excellent flame retardancy, and
maintains a constant shape when being heated.
[0018] The present inventors conducted intensive research, and as a
result, they found that a flame-retardant urethane resin
composition containing a polyisocyanate compound, a polyol
compound, a trimerization catalyst, a foaming agent, a foam
stabilizer, and an additive which contains red phosphorus as an
essential component may be used in embodiments according to the
disclosure.
[0019] One or more aspects of the present disclosure provide a
flame-retardant urethane, resin composition comprising: a
polyisocyanate compound; a polyol compound; a trimerization
catalyst; a foaming agent; a foam stabilizer; and an additive,
wherein the trimerization catalyst is at least one selected from
the group consisting of a nitrogen-containing aromatic compound, a
carboxylic acid alkali metal salt, a tertiary ammonium salt, and a
quaternary ammonium salt, and the additive comprises red phosphorus
and at least one selected from the group consisting of a phosphoric
acid ester, a phosphate-containing flame retardant, a
bromine-containing flame retardant, a boron-containing flame
retardant, an antimony-containing flame retardant, and a metal
hydroxide.
[0020] One or more aspects of the present disclosure provide foam
obtained by molding the flame-retardant urethane resin
composition.
[0021] One or more aspects of the present disclosure provide a
covered flame-retardant structure obtained by covering a structure
with the flame-retardant urethane resin composition.
[0022] One or more aspects of the present disclosure provide a
method for producing a flame-retardant urethane resin composition
comprises: preparing an additive by mixing red phosphorus and at
least one selected from the group consisting of a phosphoric acid
ester, a phosphate-containing flame retardant, a bromine-containing
flame retardant, a boron-containing flame retardant, an
antimony-containing flame retardant, and a metal hydroxide;
preparing a mixture by mixing a polyol compound, a trimerization
catalyst, a forming agent, a foam stabilizer, and the additive; and
adding a polyisocyanate compound into the mixture, wherein the
trimerization catalyst is at least one selected from the group
consisting of a nitrogen-containing aromatic compound, a carboxylic
acid alkali metal salt, a tertiary ammonium salt, and a quaternary
ammonium salt.
[0023] According to one or more embodiments of the present
disclosure, it is possible to provide a flame-retardant urethane
resin composition capable of forming foam that can be handled
easily, has excellent flame retardancy, and maintains a constant
shape when being heated.
DETAILED DESCRIPTION OF EMBODIMENTS
[0024] A flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure will be
described.
[0025] First, a urethane resin used in the flame-retardant urethane
resin composition will be described.
[0026] The urethane resin is composed of a polyisocyanate compound
as a main agent and a polyol compound as a curing agent.
[0027] Examples of the polyisocyanate compound as a main agent of
the urethane resin include an aromatic polyisocyanate, an alicyclic
polyisocyanate, an aliphatic polyisocyanate, and the like.
[0028] Examples of the aromatic polyisocyanate include phenylene
diisocyanate, tolylene diisocyanate, xylylene diisocyanate,
diphenylmethane diisocyanate, dimethyl diphenylmethane
diisocyanate, triphenylmethane triisocyanate, naphthalene
diisocyanate, polymethylene polyphenyl polyisocyanate, and the
like.
[0029] Examples of the alicyclic polyisocyanate include
cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate,
isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyl
dicyclohexylmethane diisocyanate, and the like.
[0030] Examples of the aliphatic polyisocyanate include methylene
diisocyanate, ethylene diisocyanate, propylene diisocyanate,
tetramethylene diisocyanate, hexamethylene diisocyanate, and the
like.
[0031] One kind of the polyisocyanate compound or two or more kinds
thereof can be used.
[0032] As the main agent of the urethane resin used in one or more
embodiments of the present disclosure, diphenylmethane diisocyanate
is preferable because it is easy to use and easily available.
[0033] Examples of the polyol compound as a curing agent of the
urethane resin include polylactone polyol, polycarbonate polyol,
aromatic polyol, alicyclic polyol, aliphatic polyol, polyester
polyol, polymer polyol, polyether polyol, and the like.
[0034] Examples of the polylactone polyol include polypropiolactone
glycol, polycaprolactone glycol, polyvalerolactone glycol, and the
like.
[0035] Examples of the polycarbonate polyol include polyols
obtained by a dealcoholization reaction between a hydroxyl
group-containing compound, such as ethylene glycol, propylene
glycol, butanediol, pentanediol, hexanediol, octanediol, or
nonanediol, and diethylene carbonate, dipropylene carbonate, or the
like.
[0036] Examples of the aromatic polyol include bisphenol A,
bisphenol F, phenol novolac, cresol novolac, and the like.
[0037] Examples of the alicyclic polyol include cyclohexanediol,
methyl cyclohexanediol, isophorone diol, dicyclohexyl methanediol,
dimethyl dicyclohexyl methanediol, and the like.
[0038] Examples of the aliphatic polyol include ethylene glycol,
propylene glycol, butanediol, pentanediol, hexanediol, and the
like.
[0039] Examples of the polyester polyol include a polymer obtained
by dehydration condensation of a polybasic acid and a polyhydric
alcohol, a polymer obtained by ring opening polymerization of a
lactone such as .epsilon.-caprolactone or
.alpha.-methyl-.epsilon.-caprolactone, and a condensate of a
hydroxycarboxylic acid, the aforementioned polyhydric alcohol, and
the like.
[0040] Examples of the polybasic acid specifically include adipic
acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic
acid, succinic acid, and the like.
[0041] Examples of the polyhydric alcohol specifically include
bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol,
diethylene glycol, 1,6-hexane glycol, neopentyl glycol, and the
like.
[0042] Examples of the hydroxycarboxylic acid specifically include
castor oil, a reaction product from castor oil and ethylene glycol,
and the like.
[0043] Examples of the polymer polyol include polymers obtained by
graft-polymerizing the aforementioned aromatic polyol, alicyclic
polyol, aliphatic polyol, polyester polyol, or the like with an
ethylenically unsaturated compound such as acrylonitrile, styrene,
methyl acrylate, or methacrylate, polybutadiene polyol, modified
polyol of a polyhydric alcohol, hydrogenated substances of these,
and the like.
[0044] Examples of the modified polyol of a polyhydric alcohol
include those obtained by modifying the polyhydric alcohol as a raw
material by reacting the polyhydric alcohol with an alkylene
oxide.
[0045] Examples of the polyhydric alcohol include a trihydric
alcohol such as glycerin and trimethylolpropane; alcohols having 4
to 8 hydroxyl groups such as pentaerythritol, sorbitol, mannitol,
sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose,
fructose, methyl glucoside, derivatives of these; phenols such as
phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone,
bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene,
1,3,6,8-tetrahydroxynaphthalene, anthrol,
1,4,5,8-tetrahydroxyanthracene, and 1-hydroxypyrene; polybutadiene
polyol; castor oil polyol; polyfunctional polyols (for example,
having 2 to 100 functional groups) such as a (co)polymer of
hydroxyalkyl (meth)acrylate and polyvinyl alcohol; and a condensate
(novolac) of phenol and formaldehyde.
[0046] The method for modifying the polyhydric alcohol is not
particularly limited. However, a method of adding alkylene oxide
(hereinafter, abbreviated to AO) to the polyhydric alcohol is
preferably used.
[0047] Examples of the AO include an AO having 2 to 6 carbon atoms,
such as ethylene oxide (hereinafter, abbreviated to EO),
1,2-propylene oxide (hereinafter, abbreviated to PO), 1,3-propylene
oxide, 1,2-butylene oxide, and 1,4-butylene oxide.
[0048] Among these, from the viewpoint of the properties and
reactivity, PO, EO, and 1,2-butylene oxide are preferable, and PO
and EO are more preferable.
[0049] When two or more kinds of AO (for example, PO and EO) are
used, they may be added to the polyhydric alcohol by a method in
which they are added in the form of a block copolymer or a random
copolymer. Alternatively, a block copolymer and a random copolymer
may be concurrently used.
[0050] Examples of the polyether polyol include a polymer which is
obtained by performing ring-opening polymerization of at least one
kind of alkylene oxide such as ethylene oxide, propylene oxide, or
tetrahydrofuran in the presence of at least one kind of compound
such as a low-molecular weight active hydrogen compound having 2 or
more active hydrogen atoms.
[0051] Examples of the low-molecular weight active hydrogen
compound having 2 or more active hydrogen atoms include diols such
as bisphenol A, ethylene glycol, propylene glycol, butylene glycol,
and 1,6-hexanediol; triols such as glycerin and trimethylolpropane;
amines such as ethylenediamine and butylenediamine; and the
like.
[0052] In one or more embodiments of the present disclosure, it is
preferable to use polyester polyol or polyether polyol as the
polyol because they exert a strong effect of reducing a gross
calorific value at the time of combustion.
[0053] Particularly, a polyester polyol having a molecular weight
of 200 to 800 is preferably used, and a polyester polyol having a
molecular weight of 300 to 500 is more preferably used.
[0054] An isocyanate index is a measure determined by expressing an
equivalent ratio of an isocyanate group of a polyisocyanate
compound to a hydroxyl group of a polyol compound by a percentage.
If a value of the index is greater than 100, this means that the
amount of the isocyanate group is greater than the amount of the
hydroxyl group.
[0055] The isocyanate index of the urethane resin used in one or
more embodiments of the present disclosure is preferably within a
range of 120 to 1,000, more preferably within a range of 200 to
800, and even more preferably within a range of 300 to 600.
[0056] The flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure further contains
a catalyst, a foam stabilizer, and a foaming agent.
[0057] Examples of the catalyst include triethylamine,
N-methylmorpholine bis(2-dimethylaminoethyl)ether,
N,N,N',N'',N''-pentamethyl diethylenetriamine,
N,N,N'-trimethylaminoethyl ethanolamine,
bis(2-dimethylaminoethyl)ether, N-methyl,N'-dimethylaminoethyl
piperazine, a nitrogen atom-containing catalyst such as an
imidazole compound obtained by substituting a secondary amine
functional group in an imidazole ring with a cyanoethyl group, and
the like.
[0058] The amount of the catalyst added to the flame-retardant
urethane resin composition according to one or more embodiments of
the present disclosure is preferably within a range of 0.6 parts by
weight to 10 parts by weight, more preferably within a range of 0.6
parts by weight to 8 parts by weight, even more preferably within a
range of 0.6 parts by weight to 6 parts by weight, and most
preferably within a range of 0.6 parts by weight to 3.0 parts by
weight, with respect to 100 parts by weight of the urethane
resin.
[0059] In selected embodiments, the catalyst added is equal to or
greater than 0.6 parts by weight to equal to or less than 10 parts
by weight. An appropriate foaming rate can be maintained, and thus
the foam is handled easily.
[0060] The catalyst used in one or more embodiments of the present
disclosure includes a trimerization catalyst that accelerates the
generation of an isocyanurate ring by reacting and trimerizing the
isocyanate group contained in the polyisocyanate compound as a main
agent of a polyurethane resin.
[0061] In order to accelerate the generation of an isocyanurate
ring, it is possible to use a catalyst like a nitrogen-containing
aromatic compound such as tris(dimethylaminomethyl)phenol,
2,4-bis(dimethylaminomethyl)phenol, or
2,4,6-tris(dialkylaminoalkyl)hexahydro-s-triazine; a carboxylic
acid alkali metal salt such as potassium acetate, potassium
2-ethylhexanoate, or potassium octylate; a tertiary ammonium salt
such as a trimethyl ammonium salt, a triethyl ammonium salt, or a
triphenyl ammonium salt; a quaternary ammonium salt such as a
tetramethyl ammonium salt, tetraethyl ammonium salt, or a
tetraphenyl ammonium salt; and the like.
[0062] The amount of the trimerization catalyst added to the
flame-retardant urethane resin composition according to one or more
embodiments of the present disclosure is preferably within a range
of 0.6 parts by weight to 10 parts by weight, more preferably
within a range of 0.6 by weight to 8 parts by weight, even more
preferably within a range of 0.6 parts by weight to 6 parts by
weight, and most preferably within a range of 0.6 parts by weight
to 3.0 parts by weight, with respect to 100 parts by weight of the
urethane resin.
[0063] In selected embodiments, the trimerization catalyst added is
equal to or greater than 0.6 parts by weight to equal to or less
than 10 parts by weight. An appropriate foaming rate can be
maintained, and thus the foam is handled easily.
[0064] The foaming agent used in the flame-retardant urethane resin
composition according to one or more embodiments of the present
disclosure accelerates foaming of the urethane resin.
[0065] Specific examples of the foaming agent include water,
low-boiling point hydrocarbons such as propane, butane, pentane,
hexane, heptane, cyclopropane, cyclobutane, cyclopentane,
cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon
compounds such as dichloroethane, propyl chloride, isopropyl
chloride, butyl chloride, isobutyl chloride, pentyl chloride, and
isopentyl chloride; fluorine compounds such as
trichloromonofluoromethane and trichlorotrifluoroethane;
hydrofluorocarbons such as CHF.sub.3, CH.sub.2F.sub.2, and
CH.sub.3F; hydrochlorofluorocarbon compounds such as
dichloromonofluoroethane (for example, HCFC141b
(1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), or
HCFC142b (1-chloro-1,1-difluoroethane)), HFC-245fa
(1,1,1,3,3-pentafluoropropane), and HFC-365mfc
(1,1,1,3,3-pentafluorobutane); an ether compound such as
diisopropylether; an organic physical foaming agent such as a
mixture of the above compounds; an inorganic physical foaming agent
such as nitrogen gas, oxygen gas, argon gas, or carbon dioxide gas;
and the like.
[0066] The amount of the foaming agent used in the flame-retardant
urethane resin composition according to one or more embodiments of
the present disclosure is preferably within a range of 0.1 parts by
weight to 30 parts by weight with respect to 100 parts by weight of
the urethane resin.
[0067] The amount of the foaming agent is more preferably within a
range of 0.1 parts by weight to 18 parts by weight, even more
preferably within a range of 0.5 parts by weight to 18 parts by
weight, and most preferably within a range of 1 part by weight to
10 parts by weight, with respect to 100 parts by weight of the
urethane resin.
[0068] In selected embodiments, if the amount of water is within a
range of equal to or greater than 0.1 parts by weight, foaming is
accelerated, and the density of the obtained molded article can be
reduced. In selected embodiments, if the amount of water is equal
to or less than 30 parts by weight, foam does not burst, and it is
possible to prevent foam from not being formed.
[0069] The flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure contains a foam
stabilizer.
[0070] Examples of the foam stabilizer include surfactants like a
polyoxyalkylene foam stabilizer such as polyoxyalkylene alkyl ether
and a silicone foam stabilizer such as organopolysiloxane, and the
like.
[0071] The amount of the foam stabilizer used with respect to the
urethane resin cured by the chemical reaction is appropriately
determined depending on the urethane resin cured by the chemical
reaction used. However, for example, the amount of the foam
stabilizer used is preferably within a range of 0.1 parts by weight
to 10 parts by weight with respect to 100 parts by weight of the
urethane resin.
[0072] One kind of each of the catalyst, the foaming agent, and the
foam stabilizer can be used, or two or more kinds thereof can be
used.
[0073] Next, an additive used in one or more embodiments of the
present disclosure will be described.
[0074] The flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure contains an
additive.
[0075] The additive is obtained by combining red phosphorus as an
essential component with at least one kind selected from the group
consisting of a phosphoric acid ester, a phosphate-containing flame
retardant, a bromine-containing flame retardant, a boron-containing
flame retardant, an antimony-containing flame retardant, and a
metal hydroxide other than the red phosphorus.
[0076] The red phosphorus used in one or more embodiments of the
present disclosure is not limited, and a commercially available
product can be appropriately selected and used.
[0077] The amount of red phosphorus added that is used in the
flame-retardant urethane resin composition according to one or more
embodiments of the present disclosure is preferably within a range
of 3.0 parts by weight to 18 parts by weight with respect to 100
parts by weight of the urethane resin.
[0078] In selected embodiments, If the amount of red phosphorus
added is within a range of equal to or greater than 3.0 parts by
weight, the self-extinguishability of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is maintained, and if it is equal to or less
than 18 parts by weight, foaming of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is not hindered.
[0079] The phosphoric acid ester used in one or more embodiments of
the present disclosure is not particularly limited. However, it is
preferable to use a monophosphoric acid ester, a condensed
phosphoric acid ester, and the like.
[0080] The monophosphoric acid ester is not particularly limited,
and examples thereof include trimethyl phosphate, triethyl
phosphate, tributyl phosphate, tris(2-ethylhexyl)phosphate,
tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate,
trixylenyl phosphate, tris(isopropylphenyl)phosphate,
tris(phenylphenyl)phosphate, trinaphthyl phosphate, cresyl diphenyl
phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl)
phosphate, di(isopropylphenyl)phenyl phosphate, monoisodecyl
phosphate, 2-acryloyloxyethyl acid phosphate,
2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl
phosphate, diphenyl-2-acryloyloxyethyl phosphate,
diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate,
dimelamine phosphate, melamine pyrophosphate, triphenylphosphine
oxide, tricresylphosphine oxide, diphenyl methanephosphonate,
diethyl phenylphosphonate, resorcinol bis(diphenylphosphate),
bisphenol A bis(diphenylphosphate), phosphaphenanthrene,
tris(.beta.-chloropropyl)phosphate, and the like.
[0081] The condensed phosphoric acid ester is not particularly
limited, and examples thereof include condensed phosphoric acid
esters such as trialkyl polyphosphate, resorcinol polyphenyl
phosphate, resorcinol poly(di-2,6-xylyl)phosphate (manufactured by
DAIHACHI CHEMICAL INDUSTRY CO., LTD., trade name: PX-200),
hydroquinone poly(2,6-xylyl)phosphate, and a condensate of
these.
[0082] Examples of commercially available condensed phosphoric acid
esters include resorcinol polyphenyl phosphate (manufactured by
ADEKA CORPORATION, trade name: CR-733S), bisphenol A polycresyl
phosphate (manufactured by ADEKA CORPORATION, trade name: CR-741),
an aromatic condensed phosphoric acid ester (manufactured by ADEKA
CORPORATION, trade name: CR747), resorcinol polyphenyl phosphate
(manufactured by ADEKA CORPORATION, trade name: Adekastab PFR),
bisphenol A polycresyl phosphate (manufactured by ADEKA
CORPORATION, trade name: FP-600, EP-700, and the like.
[0083] Among the above, a monophosphoric acid ester is preferably
used because it has a strong effect of reducing viscosity of the
composition having not yet been cured and a strong effect of
reducing an initial calorific value, and
tris(.beta.-chloropropyl)phosphate is more preferably used.
[0084] One kind of the phosphoric acid ester or two or more kinds
thereof can be used.
[0085] The amount of the phosphoric acid ester added that is used
in one or more embodiments of the present disclosure is preferably
within a range of 1.5 parts by weight to 52 parts by weight, more
preferably within a range of 1.5 parts by weight to 20 parts by
weight, even more preferably within a range of 2.0 parts by weight
to 15 parts by weight, and most preferably within a range of 2.0
parts by weight to 10 parts by weight, with respect to 100 parts by
weight of the urethane resin.
[0086] If the amount of the phosphoric acid ester added is within a
range of equal to or greater than 1.5 parts by weight, the molded
article formed of the flame-retardant urethane resin composition
according to one or more embodiments of the present disclosure can
prevent dense residues formed by heat resulting from fire from
cracking. If the amount of the phosphoric acid ester added is
within a range of equal to or less than 52 parts by weight, foaming
of the flame-retardant urethane resin composition according to one
or more embodiments of the present disclosure is not hindered.
[0087] The phosphate-containing flame retardant used in one or more
embodiments of the present disclosure contains phosphoric acid.
[0088] The phosphoric acid used in the phosphate-containing flame
retardant is not particularly limited, and examples thereof include
various phosphoric acids such as monophosphoric acid,
pyrophosphoric acid, and polyphosphoric acid.
[0089] Examples of the phosphate-containing flame retardant include
phosphates composed of a salt of the aforementioned various
phosphoric acids and at least one kind of metal or compound
selected from among metals of groups IA to IVB in the periodic
table, ammonia, an aliphatic amine, and an aromatic amine.
[0090] Examples of the metal of groups IA to IVB in the periodic
table include lithium, sodium, calcium, barium, iron(II),
iron(III), aluminum, and the like.
[0091] Examples of the aliphatic amine include methylamine,
ethylamine, diethylamine, triethylamine, ethylenediamine,
piperazine, and the like.
[0092] Examples of the aromatic amine include pyridine, triazine,
melamine, ammonium, and the like.
[0093] The phosphate-containing flame retardant may be treated by a
known method so as to improve waterproofing properties thereof,
such as being treated with a silane coupling agent or being covered
with a melamine resin. Furthermore, a known foaming adjuvant such
as melamine or pentaerythritol may be added thereto.
[0094] Specific examples of the phosphate-containing flame
retardant include a monophosphate, a pyrophosphate, a
polyphosphate, and the like.
[0095] The monophosphate is not particularly limited, and examples
thereof include an ammonium salt such as ammonium phosphate,
ammonium dihydrogen phosphate, or diammonium hydrogen phosphate; a
sodium salt such as monosodium phosphate, disodium phosphate,
trisodium phosphate, monosodium phosphite, disodium phosphite, or
sodium hypophosphite; a potassium salt such as monopotassium
phosphate, dipotassium phosphate, tripotassium phosphate,
monopotassium phosphite, dipotassium phosphite, or potassium
hypophosphite; a lithium salt such as monolithium phosphate,
dilithium phosphate, trilithium phosphate, monolithium phosphite,
dilithium phosphite, or lithium hypophosphite; a barium salt such
as barium dihydrogen phosphate, barium hydrogen phosphate,
tribarium phosphate, or barium hypophosphite; a magnesium salt such
as magnesium dihydrogen phosphate, magnesium hydrogen phosphate,
trimagnesium phosphate, or magnesium hypophosphite; a calcium salt
such as calcium dihydrogen phosphate, calcium hydrogen phosphate,
tricalcium phosphate, or calcium hypophosphite; a zinc salt such as
zinc phosphate, zinc phosphite, or zinc hypophosphite; and the
like.
[0096] The polyphosphate is not particularly limited, and examples
thereof include ammonium polyphosphate, piperazine polyphosphate,
melamine polyphosphate, ammonium amide polyphosphate, aluminum
polyphosphate, and the like.
[0097] Among these, a monophosphate is preferably used, and
ammonium dihydrogen phosphate is more preferably used, because the
self-extinguishability of the phosphate-containing flame retardant
is improved.
[0098] One kind of the phosphate-containing flame retardant or two
or more kinds thereof can be used.
[0099] The amount of the phosphate-containing flame retardant added
that is used in one or more embodiments of the present disclosure
is preferably within a range of 1.5 parts by weight to 52 parts by
weight, more preferably within a range of 1.5 parts by weight to 20
parts by weight, even more preferably within a range of 2.0 parts
by weight to 15 parts by weight, and most preferably within a range
of 2.0 parts by weight to 10 parts by weight, with respect to 100
parts by weight of the urethane resin.
[0100] If the amount of the phosphate-containing flame retardant
added is within a range of equal to or greater than 1.5 parts by
weight, the self-extinguishability of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is maintained, and if it is equal to or less
than 52 parts by weight, foaming of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is not hindered.
[0101] The bromine-containing flame retardant used in one or more
embodiments of the present disclosure is not particularly limited
as long as it is a compound containing bromine in a molecular
structure thereof. Examples thereof include an aromatic brominated
compound and the like.
[0102] Specific examples of the aromatic brominated compound
include a monomeric organic bromine compound such as
hexabromobenzene, pentabromotoluene, hexabromobiphenyl,
decabromobiphenyl, hexabromocyclodecane, decabromodiphenylether,
octabromodiphenylether, hexabromodiphenylether,
bis(pentabromophenoxy)ethane, ethylene bis(tetrabromophthalimide),
and tetrabromobisphenol A; a brominated polycarbonate such as a
polycarbonate oligomer manufactured by using brominated bisphenol A
as a raw material and a copolymer of the polycarbonate oligomer and
bisphenol A; brominated epoxy compounds such as a diepoxy compound
manufactured by a reaction between brominated bisphenol A and
epichlorohydrin and a monoepoxy compound obtained by a reaction
between brominated phenols and epichlorohydrin; poly(brominated
benzyl acrylate); brominated polyphenylene ether; a condensate of
brominated bisphenol A, cyanuric chloride, and brominated phenol;
brominated polystyrene such as brominated (polystyrene),
poly(brominated styrene), and crosslinked brominated polystyrene;
and a halogenated bromine compound polymer such as crosslinked or
non-crosslinked brominated poly(methylstyrene).
[0103] From the viewpoint of controlling the calorific value at the
initial stage of combustion, brominated polystyrene,
hexabromobenzene, and the like are preferable, and hexabromobenzene
is more preferable.
[0104] One kind of the bromine-containing flame retardant or two or
more kinds thereof can be used.
[0105] The amount of the bromine-containing flame retardant added
that is used in one or more embodiments of the present disclosure
is preferably within a range of 1.5 parts by weight to 52 parts by
weight, more preferably within a range of 1.5 parts by weight to 20
parts by weight, even more preferably within a range of 2.0 parts
by weight to 15 parts by weight, and most preferably within a range
of 2.0 parts by weight to 10 parts by weight, with respect to 100
parts by weight of the urethane resin.
[0106] If the amount of the bromine-containing flame retardant
added is within a range of equal to or greater than 0.1 parts by
weight, the self-extinguishability of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is maintained, and if it is equal to or less
than 52 parts by weight, foaming of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is not hindered.
[0107] Examples of the boron-containing flame retardant used in one
or more embodiments of the present disclosure include borax, boron
oxide, boric acid, borate, and the like.
[0108] Examples of the boron oxide include diboron trioxide, boron
trioxide, diboron dioxide, tetraboron trioxide, tetraboron
pentoxide, and the like.
[0109] Examples of the borate include a borate of an alkali metal,
a borate of an alkaline earth metal, a borate of an element of
group 4, group 12, or group 13 in the periodic table, a borate of
ammonium, and the like.
[0110] Specifically, examples of the borate include an alkali metal
salt borate such as lithium borate, sodium borate, potassium
borate, and cesium borate; an alkaline earth metal salt borate such
as magnesium borate, calcium borate, and barium borate; zirconium
borate; zinc borate; aluminum borate; ammonium borate; and the
like.
[0111] The boron-containing flame retardant used in one or more
embodiments of the present disclosure is preferably a borate and
more preferably zinc borate.
[0112] One kind of the boron-containing flame retardant or two or
more kinds thereof can be used.
[0113] The amount of the boron-containing flame retardant added
that is used in one or more embodiments of the present disclosure
is preferably within a range of 1.5 parts by weight to 52 parts by
weight, more preferably within a range of 1.5 parts by weight to 20
parts by weight, even more preferably within a range of 2.0 parts
by weight to 15 parts by weight, and most preferably within a range
of 2.0 parts by weight to 10 parts by weight, with respect to 100
parts by weight of the urethane resin.
[0114] If the amount of the boron-containing flame retardant added
is within a range of equal to or greater than 1.5 parts by weight,
the self-extinguishability of the flame-retardant urethane resin
composition according to one or more embodiments of the present
disclosure is maintained, and if it is equal to or less than 52
parts by weight, foaming of the flame-retardant urethane resin
composition according to one or more embodiments of the present
disclosure is not hindered.
[0115] Examples of the antimony-containing flame retardant used in
one or more embodiments of the present disclosure include antimony
oxide, an antimonate, a pyroantimonate, and the like.
[0116] Examples of the antimony oxide include antimony trioxide,
antimony pentoxide, and the like.
[0117] Examples of the antimonate include sodium antimonate,
potassium antimonate, and the like.
[0118] Examples of the pyroantimonate include sodium
pyroantimonate, potassium pyroantimonate, and the like.
[0119] The antimony-containing flame retardant used in one or more
embodiments of the present disclosure is preferably antimony
oxide.
[0120] One kind of the antimony-containing flame retardant or two
or more kinds thereof can be used.
[0121] The amount of the antimony-containing flame retardant added
that is used in one or more embodiments of the present disclosure
is preferably within a range of 1.5 parts by weight to 52 parts by
weight, more preferably within a range of 1.5 parts by weight to 20
parts by weight, even more preferably within a range of 2.0 parts
by weight to 15 parts by weight, and most preferably within a range
of 2.0 parts by weight to 10 parts by weight, with respect to 100
parts by weight of the urethane resin.
[0122] If the amount of the antimony-containing flame retardant
added is within a range of equal to or greater than 1.5 parts by
weight, the self-extinguishability of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is maintained, and if it is equal to or less
than 52 parts by weight, foaming of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is not hindered.
[0123] Examples of the metal hydroxide used in one or more
embodiments of the present disclosure include magnesium hydroxide,
calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel
hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide,
copper hydroxide, vanadium hydroxide, tin hydroxide, and the
like.
[0124] One kind of the metal hydroxide or two or more kinds thereof
can be used.
[0125] The amount of the metal hydroxide added that is used in one
or more embodiments of the present disclosure is preferably within
a range of 1.5 parts by weight to 52 parts by weight, more
preferably within a range of 1.5 parts by weight to 20 parts by
weight, even more preferably within a range of 2.0 parts by weight
to 15 parts by weight, and most preferably within a range of 2.0
parts by weight to 10 parts by weight, with respect to 100 parts by
weight of the urethane resin.
[0126] If the amount of the metal hydroxide added is within a range
of equal to or greater than 1.5 parts by weight, the
self-extinguishability of the flame-retardant urethane resin
composition according to one or more embodiments of the present
disclosure is maintained, and if it is equal to or less than 52
parts by weight, foaming of the flame-retardant urethane resin
composition according to one or more embodiments of the present
disclosure is not hindered.
[0127] The flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure can also contain
an inorganic filler.
[0128] The inorganic filler is not particularly limited, and
examples thereof include silica, diatomite, alumina, titanium
oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide,
antimony oxide, ferrites, basic magnesium carbonate, calcium
carbonate, magnesium carbonate, zinc carbonate, barium carbonate,
dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum
fiber, a calcium salt such as calcium silicate, talc, clay, mica,
montmorillonite, bentonite, activated white earth, sepiolite,
imogolite, sericite, glass fibers, glass beads, a silica balloon,
aluminum nitride, boron nitride, silicon nitride, carbon black,
graphite, carbon fibers, a carbon balloon, charcoal powder, various
metal powders, potassium titanate, magnesium sulfate, lead
zirconate titanate, aluminum borate, molybdenum sulfide, silicon
carbide, stainless steel fibers, various magnetic powders, slag
fibers, fly ash, silica alumina fibers, alumina fibers, silica
fibers, zirconia fibers, and the like.
[0129] One kind of the inorganic filler or two or more kinds
thereof can be used.
[0130] If necessary, the flame-retardant urethane resin composition
according to one or more embodiments of the present disclosure can
contain an additive such as an antioxidant based on phenol, amine,
or sulfur, a light stabilizer, a metal deterioration inhibitor, an
antistatic agent, a stabilizer, a crosslinking agent, a lubricant,
a softener, a pigment, or a tackifying resin and an adhesiveness
imparting agent such as polybutene or a petroleum resin, within a
range that does not impair the object of the present
disclosure.
[0131] The additive used in one or more embodiments of the present
disclosure is obtained by combining red phosphorus as an essential
component with at least one kind selected from the group consisting
of the phosphoric acid ester, the phosphate-containing flame
retardant, the bromine-containing flame retardant, the
boron-containing flame retardant, the antimony-containing flame
retardant, and the metal hydroxide other than the red
phosphorus.
[0132] Examples of a preferred combination for the additive used in
one or more embodiments of the present disclosure include any of
the following (a) to (n).
[0133] (a) Red phosphorus and phosphoric acid ester
[0134] (b) Red phosphorus and phosphate-containing flame
retardant
[0135] (c) Red phosphorus and bromine-containing flame
retardant
[0136] (d) Red phosphorus and boron-containing flame retardant
[0137] (e) Red phosphorus and antimony-containing flame
retardant
[0138] (f) Red phosphorus and metal hydroxide
[0139] (g) Red phosphorus, phosphoric acid ester, and
phosphate-containing flame retardant
[0140] (h) Red phosphorus, phosphoric acid ester, and
bromine-containing flame retardant
[0141] (i) Red phosphorus, phosphoric acid ester, and
boron-containing flame retardant
[0142] (j) Red phosphorus, phosphate-containing flame retardant,
and bromine-containing flame retardant
[0143] (k) Red phosphorus, phosphate-containing flame retardant,
and boron-containing flame retardant
[0144] (l) Red phosphorus, bromine-containing flame retardant, and
boron-containing flame retardant
[0145] (m) Red phosphorus, phosphoric acid ester,
phosphate-containing flame retardant, and bromine-containing flame
retardant
[0146] (n) Red phosphorus, phosphoric acid ester,
phosphate-containing flame retardant, bromine-containing flame
retardant, and boron-containing flame retardant
[0147] The total amount of the added additive other than the
urethane resin that is used in one or more embodiments of the
present disclosure is preferably within a range of 4.5 parts by
weight to 70 parts by weight, more preferably within a range of 4.5
parts by weight to 40 parts by weight, even more preferably within
a range of 4.5 parts by weight to 30 parts by weight, and most
preferably within a range of 4.5 parts by weight to 20 parts by
weight, with respect to 100 parts by weight of the urethane
resin.
[0148] If the amount of the additive added is within a range of
equal to or greater than 4.5 parts by weight, the molded article
formed of the flame-retardant urethane resin composition according
to one or more embodiments of the present disclosure can prevent
dense residues formed by heat resulting from fire from being
broken. If the amount of the additive added is equal to or less
than 70 parts by weight, foaming of the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is not hindered.
[0149] The flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure is cured by a
reaction. Accordingly, the viscosity thereof changes over time.
[0150] Therefore, before being used, the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure is separated into 2 or more fractions so as to
prevent the flame-retardant urethane resin composition from being
cured by a reaction. The flame-retardant urethane resin composition
according to one or more embodiments of the present disclosure that
has been separated into 2 or more fractions is combined at the time
of use, and in this way, the flame-retardant urethane resin
composition according to one or more embodiments of the present
disclosure is obtained.
[0151] At the time of separating the flame-retardant urethane resin
composition into 2 or more fractions, components of each fraction
of the flame-retardant urethane resin composition having been
separated into 2 or more fractions may be separated, such that the
components of each fraction of the flame-retardant urethane resin
composition having been separated into 2 or more fractions do not
start to be cured independently, and the curing reaction starts
after the components of the flame-retardant urethane resin
composition are mixed together.
[0152] Next, the method for manufacturing the flame-retardant
urethane resin composition according to one or more embodiments of
the present disclosure will be described.
[0153] The method for manufacturing the flame-retardant urethane
resin composition is not particularly limited. For example, the
flame-retardant urethane resin composition can be obtained by a
method of mixing the respective components of the flame-retardant
urethane resin composition together, a method of manufacturing the
flame-retardant urethane resin composition in the form of a coating
material by means of suspending the flame-retardant urethane resin
composition in an organic solvent or melting the flame-retardant
urethane resin composition by heating, a method of preparing a
slurry by dispersing the flame-retardant urethane resin composition
in a solvent, or a method of melting the flame-retardant urethane
resin composition by heating when the reactive curable resin
component contained in the flame-retardant urethane resin
composition contains a component which stays in a solid state at a
temperature of 25.degree. C.
[0154] The flame-retardant urethane resin composition can be
obtained by kneading the respective components thereof by using a
known apparatus such as a single screw extruder, a twin screw
extruder, a Banbury mixer, a kneader mixer, a kneading roll, a
Raikai mixer, or a planetary stirrer.
[0155] The flame-retardant urethane resin composition can also be
obtained by mixing each of the main agent of the urethane resin and
the curing agent with a filler or the like in advance, and then
kneading the mixture by using a static mixer, a dynamic mixer, or
the like immediately before the mixture is injected into a
vessel.
[0156] Furthermore, the flame-retardant urethane resin composition
can be obtained by kneading the components of the flame-retardant
urethane resin composition excluding the catalyst and the catalyst
in the same manner as described above immediately before the
components are injected into a vessel.
[0157] The flame-retardant urethane resin composition according to
one or more embodiments of the present disclosure can be obtained
by the methods described above.
[0158] Next, the method for curing the flame-retardant urethane
resin composition according to one or more embodiments of the
present disclosure will be described.
[0159] When the respective components of the flame-retardant
urethane resin composition are mixed together, a reaction starts,
viscosity thereof increases over time, and as a result, the
composition loses fluidity.
[0160] For example, by curing the flame-retardant urethane resin
composition by means of injecting it into a vessel such as a mold
or a frame material, a molded article formed of the flame-retardant
urethane resin composition can be obtained in the form of foam.
[0161] For obtaining the molded article formed of the
flame-retardant urethane resin composition, heat or pressure can be
applied to the composition.
[0162] A specific gravity of the molded article formed of the
flame-retardant urethane resin composition is preferably within a
range of 0.030 to 0.130, because the molded article is handled
easily. The specific gravity is more preferably within a range of
0.040 to 0.100, even more preferably within a range of 0.040 to
0.080, and most preferably within a range of 0.050 to 0.060.
[0163] Next, examples of the application of the flame-retardant
urethane resin composition according to one or more embodiments of
the present disclosure will be described.
[0164] If the flame-retardant urethane resin composition is sprayed
to structures such as buildings, furniture, automobiles, trams, and
ships, a foam layer formed of the flame-retardant urethane resin
composition can be formed on the surface of the structures.
[0165] Examples of the method for forming the foam layer include a
method of separating the flame-retardant urethane resin composition
into the polyisocyanate compound and other components in advance,
and then spraying the polyisocyanate compound and other components
onto the surface of the structure while mixing them together by
spraying, a method of mixing the polyisocyanate compound and other
components together and then spraying them onto the surface of the
structure, and the like.
[0166] By the aforementioned method, the foam layer can be formed
on the surface of the structure.
[0167] Next, a fireproof test performed on the molded article
formed of the flame-retardant urethane resin composition will be
described.
[0168] The molded article formed of the flame-retardant urethane
resin composition is cut to 10 cm (length).times.10 cm
(width).times.5 cm (thickness), thereby preparing samples for a
cone calorimeter test.
[0169] By using the samples of a cone calorimeter test, it is
possible to measure a gross calorific value of the samples, which
are heated for 20 minutes at an intensity of radiant heat of 50
kW/m.sup.2, by a cone calorimeter test based on the test method of
ISO-5660.
[0170] Hereinafter, one or more embodiments of the present
disclosure will be specifically described based on examples, but
the present disclosure is not limited to the following
examples.
Example 1
[0171] As shown in the formulation in Table 1, a flame-retardant
urethane resin composition according to Example 1 was prepared by
being separated into 3 fractions including components (A) to (C).
Herein, the details of the respective components shown in Tables 1
to 10 are as follows.
[0172] Component (A): polyol compound
[0173] (a) Polyol compound
[0174] A-1: polyol 1
[0175] p-Phthalic acid polyester polyol (manufactured by KAWASAKI
KASEI CHEMICALS LTD., trade name: Maximol RFK-505, hydroxyl
value=250 mgKOH/g)
[0176] A-2: polyol 2
[0177] o-Phthalic acid polyester polyol (manufactured by KAWASAKI
KASEI CHEMICALS LTD., trade name: Maximol RDK-142, hydroxyl
value=400 mgKOH/g)
[0178] A-3: polyol 3
[0179] o-Phthalic acid polyester polyol (manufactured by KAWASAKI
KASEI CHEMICALS LTD., trade name: Maximol RDK-121, hydroxyl
value=260 mgKOH/g)
[0180] A-4: polyol 4
[0181] p-Phthalic acid polyester polyol (manufactured by KAWASAKI
KASEI CHEMICALS LTD., trade name: Maximol RLK-035, hydroxyl
value=150 mgKOH/g)
[0182] A-5: polyol 5
[0183] Polyether polyol (manufactured by Mitsui Chemicals, Inc.,
trade name: Actcol T-400, hydroxyl value=399 mgKOH/g)
[0184] A-6: polyol 6
[0185] Polyether polyol (manufactured by Mitsui Chemicals, Inc.,
trade name: Actcol T-700, hydroxyl value=250 mgKOH/g)
[0186] A-7: polyol 7
[0187] Polyether polyol (manufactured by Mitsui Chemicals, Inc.,
trade name: Actcol GR84T, hydroxyl value=454 mgKOH/g)
[0188] A-8: polyol 8
[0189] Polyether polyol (manufactured by Mitsui Chemicals, Inc.,
trade name: Actcol SOR400, hydroxyl value=397 mgKOH/g)
[0190] (b) Foam stabilizer
[0191] Foam stabilizer containing polyalkylene glycol (manufactured
by Dow Corning Toray Co., Ltd., trade name: SH-193)
[0192] (c) Catalyst
[0193] [Trimerization catalyst]
[0194] B-1: potassium 2-ethylhexanoate (manufactured by Tokyo
Chemical Industry Co., Ltd., product code: P0048)
[0195] B-2: trimerization catalyst (manufactured by TOSOH
CORPORATION, trade name: TOYOCAT-TR20)
[0196] B-3: trimerization catalyst (manufactured by TOET CHEMICAL
INDUSTRY CO., LTD., trade name: hexoate potassium 15%)
[0197] [Urethanization catalyst]
[0198] Pentamethyldiethylenetriamine (manufactured by TOSOH
CORPORATION, trade name: TOYOCAT-DT)
[0199] (d) Foaming agent
[0200] Water
[0201] HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by
Central Glass Co., Ltd.)
[0202] HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by
Solvay Japan)
[0203] Mixing ratio: HFC-365mfc:HFC-245fa=7:3 (weight ratio,
hereinafter, referred to as "HFC")
[0204] Pentane
[0205] Component (B): isocyanate compound (hereinafter, referred to
as "polyisocyanate")
[0206] MDI (manufactured by Nippon Polyurethane Industry Co., Ltd.,
trade name: Millionate MR-200), viscosity: 167 mPas
[0207] Component (C): additive
[0208] C-1: red phosphorus (manufactured by RIN KAGAKU KOGYO Co.,
Ltd., trade name: RINKA_FE140)
[0209] C-2: ammonium dihydrogen phosphate (manufactured by Taihei
Chemical Industrial Co., Ltd.)
[0210] C-3: tris(.beta.-chloropropyl)phosphate (manufactured by
DAIHACHI CHEMICAL INDUSTRY CO., LTD., trade name: TMCPP,
hereinafter, referred to as "TMCPP")
[0211] C-4: hexabromobenzene (manufactured by Manac Incorporated,
trade name: HBB-b, hereinafter, referred to as "HBB")
[0212] C-5: zinc borate (manufactured by HAYAKAWA & CO., LTD.,
trade name: Firebrake ZB)
[0213] C-6: antimony trioxide (manufactured by NIHON SEIKO CO.,
LTD., trade name: Patox C)
[0214] C-7: aluminum hydroxide (manufactured by Almorix Co., Ltd.,
trade name: B-325)
[0215] C-8: diammonium hydrogen phosphate (manufactured by Taihei
Chemical Industrial Co., Ltd.)
[0216] C-9: aluminum phosphate monobasic (manufactured by Taihei
Chemical Industrial Co., Ltd.)
[0217] C-10: sodium phosphate monobasic (manufactured by Taihei
Chemical Industrial Co., Ltd.)
[0218] C-11: ammonium polyphosphate (manufactured by Clariant Japan
K.K., trade name: AP422)
[0219] C-12: halogen-containing condensed phosphoric acid ester
(manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD., trade name:
DAIGUARD-540)
[0220] C-13: non-halogenated condensed phosphoric acid ester
(manufactured by DAIHACHI CHEMICAL INDUSTRY CO., LTD., trade name:
CR-733S)
[0221] C-14: ethylene bis(tetrabromophthalimide) (manufactured by
ALBEMARLE CORPORATION, trade name: SAYTEX BT-93, hereinafter,
referred to as "EBTBPI")
[0222] C-15: ethylene bis(pentabromophenyl) (manufactured by
ALBEMARLE CORPORATION, trade name: SAYTEX 8010, hereinafter,
referred to as "EBPBP")
[0223] According to the formulation shown in the following Table 1,
the component (A) as a polyol compound and the component (C) as an
additive were weighed and put into a 1,000 mL polypropylene beaker
and then manually mixed and stirred together for 1 minute at
25.degree. C.
[0224] The component (B) was added to a kneaded material composed
of the component (A) and the component (C) having undergone
stirring, and the resultant was stirred for about 10 seconds by
using a hand mixer, thereby preparing foam.
[0225] The obtained flame-retardant urethane resin composition lost
fluidity with the passage of time, and foam of the flame-retardant
urethane resin composition was obtained. The foam was evaluated
based on the following criteria. The results are shown in Table
1.
[0226] [Calorific Measurement]
[0227] From the cured material, samples for a cone calorimeter test
were cut to 10 cm.times.10 cm.times.5 cm. Based on ISO-5660, the
samples were heated for 20 minutes at an intensity of radiant heat
of 50 kW/m.sup.2 so as to measure the maximum heat release rate and
the gross calorific value thereof.
[0228] The results are shown in Tables 1 to 10.
[0229] The present measurement method is a test method specified by
the General Building Research Corporation of Japan, which is a
public institution stipulated by Article 108(2) of an enforcement
decree of the Building Standard Law. The measurement method is
regarded as corresponding to the standard according to a cone
calorimeter method, and is based on the test method of
ISO-5660.
[0230] [Measurement of Expansion]
[0231] When the ISO-5660 test was performed, if an expanded molded
article came into contact with a lighter, the molded article was
evaluated to be "X", and if it did not come into contact with the
lighter, the molded article was evaluated to be "O". The results
are shown in Tables 1 to 10.
[0232] [Measurement of Deformation (Cracking)]
[0233] When the test of ISO-5660 was performed, if deformation
occurred even in the rear surface of a sample for the test, the
sample was evaluated to be "X", and if deformation did not occur in
the rear surface of a sample, the sample was evaluated to be "O".
The results are shown in Tables 1 to 10.
[0234] [Measurement of Contraction]
[0235] When the test of ISO-5660 was performed, if a sample for the
test was deformed by 1 cm or more in the width direction and by 5
mm or more in the thickness direction, the sample was evaluated to
be "X", and if a sample was not deformed, the sample was evaluated
to be "O". The results are shown in Tables 1 to 10.
[0236] [Comprehensive Evaluation]
[0237] A sample which was evaluated to be "O" in all of the
calorific measurement, the measurement of expansion, the
measurement of deformation (cracking), and the measurement of
contraction was evaluated to be "OK", and samples other than this
were evaluated to be "NG". The results are shown in Tables 1 to
10.
TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8
ple 9 ple 10 Polyol Polyol A-1 21.8 21.8 21.8 21.8 21.8 21.8 21.8
21.8 21.8 21.8 composition compound A-2 -- -- -- -- -- -- -- -- --
-- A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- -- -- -- --
-- A-5 -- -- -- -- -- -- -- -- -- -- A-6 -- -- -- -- -- -- -- -- --
-- A-7 -- -- -- -- -- -- -- -- -- -- A-8 -- -- -- -- -- -- -- -- --
-- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 stabilizer
Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 catalyst
B-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 catalyst Foaming agent Water 0.6
0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 HFC 3.9 3.9 4.6 4.8 4.7 3.7 4.7
4.7 4.7 3.7 Polyisocyanate 78.2 78.2 78.2 78.2 78.2 78.2 78.2 78.2
78.2 78.2 Additive Red C-1 3.0 6.0 12.0 18.0 10.0 6.0 13.3 10.0 4.0
3.3 phosphorus Ammonium C-2 9.0 3.0 6.0 6.0 10.0 -- -- -- -- --
dihydrogen phosphate TMCPP C-3 -- -- -- -- -- 7.0 6.7 10.0 16.0 --
HBB C-4 -- -- -- -- -- -- -- -- -- 1.7 Zinc borate C-5 -- -- -- --
-- -- -- -- -- -- Antimony C-6 -- -- -- -- -- -- -- -- -- --
trioxide Aluminum C-7 -- -- -- -- -- -- -- -- -- -- hydroxide
Density (g/cm.sup.3) 0.056 0.052 0.055 0.054 0.053 0.054 0.057
0.055 0.054 0.052 Isocyanate INDEX 400 400 400 400 400 400 400 400
400 400 Gross calorific value (MJ/m.sup.2): 3.7 2.3 3.4 6.7 7.6 3.6
4.9 4.6 6.6 7.6 after elapse of 10 minutes Gross calorific value
(MJ/m.sup.2): 5.0 4.4 5.6 7.7 11.3 7.8 8.5 6.0 9.4 10.4 after
elapse of 20 minutes Gross calorific value
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle. .largecircle.
.largecircle..largecircle. .largecircle. .largecircle..largecircle.
.largecircle. .largecircle. State of Expansion .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. residue Deformation .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. Contraction
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Determination OK OK OK OK OK OK OK OK
OK OK
Example 2
[0238] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of red
phosphorus used was changed to 6.0 parts by weight from 3.0 parts
by weight in Example 1, and the amount of ammonium dihydrogen
phosphate used was changed to 3.0 parts by weight from 9.0 parts by
weight in Example 1.
[0239] The results are shown in Table 1.
Example 3
[0240] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
foaming agent HFC used was changed to 4.6 parts by weight from 3.9
parts by weight in Example 1, the amount of red phosphorus used was
changed to 12.0 parts by weight from 3.0 parts by weight in Example
1, and the amount of ammonium dihydrogen phosphate used was changed
to 6.0 parts by weight from 9.0 parts by weight in Example 1.
[0241] The results are shown in Table 1.
Example 4
[0242] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
foaming agent HFC used was changed to 4.8 parts by weight from 3.9
parts by weight in Example 1, the amount of red phosphorus used was
changed to 18.0 parts by weight from 3.0 parts by weight in Example
1, and the amount of ammonium dihydrogen phosphate used was changed
to 6.0 parts by weight from 9.0 parts by weight in Example 1.
[0243] The results are shown in Table 1.
Example 5
[0244] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
foaming agent HFC used was changed to 4.7 parts by weight from 3.9
parts by weight in Example 1, the amount of red phosphorus used was
changed to 10.0 parts by weight from 3.0 parts by weight in Example
1, and the amount of ammonium dihydrogen phosphate used was changed
to 10.0 parts by weight from 9.0 parts by weight in Example 1.
[0245] The results are shown in Table 1.
Example 6
[0246] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
foaming agent HFC used was changed to 3.7 parts by weight from 3.9
parts by weight in Example 1, the amount of red phosphorus used was
changed to 6.0 parts by weight from 3.0 parts by weight in Example
1, and 7.0 parts by weight of TMCPP was used instead of ammonium
dihydrogen phosphate.
[0247] The results are shown in Table 1.
Example 7
[0248] The test was performed in exactly the same manner as in
Example 6, except that, compared to Example 6, the amount of the
foaming agent HFC used was changed to 4.7 parts by weight from 3.7
parts by weight in Example 6, the amount of red phosphorus used was
changed to 13.3 parts by weight from 6.0 parts by weight in Example
6, and the amount of TMCPP used was changed to 6.7 parts by weight
from 7.0 parts by weight in Example 6.
[0249] The results are shown in Table 1.
Example 8
[0250] The test was performed in exactly the same manner as in
Example 7, except that, compared to Example 7, the amount of red
phosphorus used was changed to 10.0 parts by weight from 13.3 parts
by weight in Example 7, and the amount of TMCPP used was changed to
10.0 parts by weight from 6.7 parts by weight in Example 7.
[0251] The results are shown in Table 1.
Example 9
[0252] The test was performed in exactly the same manner as in
Example 8, except that, compared to Example 8, the amount of red
phosphorus used was changed to 4.0 parts by weight from 10.0 parts
by weight in Example 8, and the amount of TMCPP used was changed to
16.0 parts by weight from 10.0 parts by weight in Example 8.
[0253] The results are shown in Table 1.
Example 10
[0254] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
foaming agent HFC used was changed to 3.7 parts by weight from 3.9
parts by weight in Example 1, the amount of red phosphorus used was
changed to 3.3 parts by weight from 3.0 parts by weight in Example
1, and 1.7 parts by weight of HBB was used instead of ammonium
dihydrogen phosphate.
[0255] The results are shown in Table 1.
Example 11
[0256] The test was performed in exactly the same manner as in
Example 10, except that, compared to Example 10, the amount of the
foaming agent HFC used was changed to 3.8 parts by weight from 3.7
parts by weight in Example 10, the amount of red phosphorus used
was changed to 6.0 parts by weight from 3.3 parts by weight in
Example 10, and the amount of HBB used was changed to 3.0 parts by
weight from 1.7 parts by weight in Example 10.
[0257] The results are shown in Table 2.
Example 12
[0258] The test was performed in exactly the same manner as in
Example 10, except that, compared to Example 10, the amount of the
foaming agent HFC used was changed to 4.5 parts by weight from 3.7
parts by weight in Example 10, the amount of red phosphorus used
was changed to 13.3 parts by weight from 3.3 parts by weight in
Example 10, and the amount of HBB used was changed to 6.7 parts by
weight from 1.7 parts by weight in Example 10.
[0259] The results are shown in Table 2.
Example 13
[0260] The test was performed in exactly the same manner as in
Example 10, except that, compared to Example 10, the amount of the
foaming agent HFC used was changed to 4.3 parts by weight from 3.7
parts by weight in Example 10, the amount of red phosphorus used
was changed to 10.0 parts by weight from 3.3 parts by weight in
Example 10, and the amount of EBB used was changed to 10.0 parts by
weight from 1.7 parts by weight in Example 10.
[0261] The results are shown in Table 2.
Example 14
[0262] The test was performed in exactly the same manner as in
Example 10, except that, compared to Example 10, the amount of the
foaming agent HFC used was changed to 4.1 parts by weight from 3.7
parts by weight in Example 10, the amount of red phosphorus used
was changed to 4.0 parts by weight from 3.3 parts by weight in
Example 10, and the amount of HBB used was changed to 16.0 parts by
weight from 1.7 parts by weight in Example 10.
[0263] The results are shown in Table 2.
Example 15
[0264] The test was performed in exactly the same manner as in
Example 11, except that, compared to Example 11, 6.0 parts by
weight of zinc borate was used instead of HBB.
[0265] The results are shown in Table 2.
Example 16
[0266] The test was performed in exactly the same manner as in
Example 11, except that, compared to Example 11, 3.0 parts by
weight of antimony trioxide was used instead of HBB.
[0267] The results are shown in Table 2.
Example 17
[0268] The test was performed in exactly the same manner as in
Example 11, except that, compared to Example 11, 3.0 parts by
weight of aluminum hydroxide was used instead of HBB.
[0269] The results are shown in Table 2.
Example 18
[0270] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of red
phosphorus used was changed to 3.8 parts by weight from 3.0 parts
by weight in Example 1, the amount of ammonium dihydrogen phosphate
used was changed to 1.9 parts by weight from 9.0 parts by weight in
Example 1, and 4.4 parts by weight of TMCPP was used.
[0271] The results are shown in Table 2.
Example 19
[0272] The test was performed in exactly the same manner as in
Example 18, except that, compared to Example 18, the amount of the
foaming agent HFC used was changed to 4.6 parts by weight from 3.9
parts by weight in Example 18, the amount of red phosphorus used
was changed to 6.0 parts by weight from 3.8 parts by weight in
Example 18, the amount of ammonium dihydrogen phosphate used was
changed to 3.0 parts by weight from 1.9 parts by weight in Example
18, and the amount of TMCPP used was changed to 7.0 parts by weight
from 4.4 parts by weight in Example 18.
[0273] The results are shown in Table 2.
Example 20
[0274] The test was performed in exactly the same manner as in
Example 19, except that, compared to Example 19, the amount of the
foaming agent HFC used was changed to 4.7 parts by weight from 4.6
parts by weight in Example 19, the amount of red phosphorus used
was changed to 7.5 parts by weight from 6.0 parts by weight in
Example 19, the amount of ammonium dihydrogen phosphate used was
changed to 3.8 parts by weight from 3.0 parts by weight in Example
19, and the amount of TMCPP used was changed to 8.8 parts by weight
from 7.0 parts by weight in Example 19.
[0275] The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 11 ple 12 ple 13 ple 14 ple 15 ple 16 ple 17
ple 18 ple 19 ple 20 Polyol Polyol A-1 21.8 21.8 21.8 21.8 21.8
21.8 21.8 21.8 21.8 21.8 composition compound A-2 -- -- -- -- -- --
-- -- -- -- A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- --
-- -- -- -- A-5 -- -- -- -- -- -- -- -- -- -- A-6 -- -- -- -- -- --
-- -- -- -- A-7 -- -- -- -- -- -- -- -- -- -- A-8 -- -- -- -- -- --
-- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 stabilizer
Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 catalyst
B-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 catalyst Foaming agent Water 0.6
0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 HFC 3.8 4.5 4.3 4.1 3.8 3.8 3.8
3.9 4.6 4.7 Polyisocyanate 78.2 78.2 78.2 78.2 78.2 78.2 78.2 78.2
78.2 78.2 Additive Red C-1 6.0 13.3 10.0 4.0 6.0 6.0 6.0 3.8 6.0
7.5 phosphorus Ammonium C-2 -- -- -- -- -- -- -- 1.9 3.0 3.8
dihydrogen phosphate TMCPP C-3 -- -- -- -- -- -- -- 4.4 7.0 8.8 HBB
C-4 3.0 6.7 10.0 16.0 -- -- -- -- -- -- Zinc borate C-5 -- -- -- --
6.0 -- -- -- -- -- Antimony C-6 -- -- -- -- -- 3.0 -- -- -- --
trioxide Aluminum C-7 -- -- -- -- -- -- 3.0 -- -- -- hydroxide
Density (g/m.sup.3) 0.052 0.050 0.056 0.053 0.051 0.050 0.051 0.055
0.055 0.055 Isocyanate INDEX 400 400 400 400 400 400 400 400 400
400 Gross calorific value (MJ/m.sup.2): 3.2 5.6 5.7 6.0 7.8 6.1 4.7
6.5 4.5 4.5 after elapse of 10 minutes Gross calorific value
(MJ/m.sup.2): 4.5 8.5 8.8 8.2 11.3 9.3 5.9 8.2 5.9 5.4 after elapse
of 20 minutes Gross calorific value .largecircle..largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle..largecircle. .largecircle.
.largecircle..largecircle. .largecircle..largecircle. State of
Expansion .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. residue Deformation .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Contraction .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Determination OK OK OK OK
OR OK OK OK OK OK
Example 21
[0276] The test was performed in exactly the same manner as in
Example 20, except that, compared to Example 20, the amount of the
foaming agent HFC used was changed to 6.4 parts by weight from 4.7
parts by weight in Example 20, the amount of red phosphorus used
was changed to 15.0 parts by weight from 7.5 parts by weight in
Example 20, the amount of ammonium dihydrogen phosphate used was
changed to 7.5 parts by weight from 3.8 parts by weight in Example
20, and the amount of TMCPP used was changed to 17.5 parts by
weight from 8.8 parts by weight in Example 20.
[0277] The results are shown in Table 3.
Example 22
[0278] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
foaming agent HFC used was changed to 3.5 parts by weight from 3.9
parts by weight in Example 1, the amount of red phosphorus used was
changed to 5.0 parts by weight from 3.0 parts by weight in Example
1, the amount of ammonium dihydrogen phosphate used was changed to
2.5 parts by weight from 9.0 parts by weight in Example 1, and 2.5
parts by weight of HBB was used.
[0279] The results are shown in Table 3.
Example 23
[0280] The test was performed in exactly the same manner as in
Example 22, except that, compared to Example 22, the amount of the
foaming agent HFC used was changed to 3.9 parts by weight from 3.5
parts by weight in Example 22, the amount of red phosphorus used
was changed to 6.0 parts by weight from 5.0 parts by weight in
Example 22, the amount of ammonium dihydrogen phosphate used was
changed to 3.0 parts by weight from 2.5 parts by weight in Example
22, and the amount of HBB used was changed to 3.0 parts by weight
from 2.5 parts by weight in Example 22.
[0281] The results are shown in Table 3.
Example 24
[0282] The test was performed in exactly the same manner as in
Example 22, except that, compared to Example 22, the amount of the
foaming agent HFC used was changed to 4.5 parts by weight from 3.5
parts by weight in Example 22, the amount of red phosphorus used
was changed to 10.0 parts by weight from 5.0 parts by weight in
Example 22, the amount of ammonium dihydrogen phosphate used was
changed to 5.0 parts by weight from 2.5 parts by weight in Example
22, and the amount of HBB used was changed to 5.0 parts by weight
from 2.5 parts by weight in Example 22.
[0283] The results are shown in Table 3.
Example 25
[0284] The test was performed in exactly the same manner as in
Example 22, except that, compared to Example 22, the amount of the
foaming agent HFC used was changed to 5.5 parts by weight from 3.5
parts by weight in Example 22, the amount of red phosphorus used
was changed to 20.0 parts by weight from 5.0 parts by weight in
Example 22, the amount of ammonium dihydrogen phosphate used was
changed to 10.0 parts by weight from 2.5 parts by weight in Example
22, and the amount of HBB used was changed to 10.0 parts by weight
from 2.5 parts by weight in Example 22.
[0285] The results are shown in Table 3.
Example 26
[0286] The test was performed in exactly the same manner as in
Example 22, except that, compared to Example 22, the amount of the
foaming agent HFC used was changed to 3.9 parts by weight from 3.5
parts by weight in Example 22, the amount of red phosphorus used
was changed to 3.8 parts by weight from 5.0 parts by weight in
Example 22, 4.4 parts by weight of TMCPP was used instead of
ammonium dihydrogen phosphate, and the amount of HBB used was
changed to 1.9 parts by weight from 2.5 parts by weight in Example
22.
[0287] The results are shown in Table 3.
Example 27
[0288] The test was performed in exactly the same manner as in
Example 26, except that, compared to Example 26, the amount of the
foaming agent HFC used was changed to 4.4 parts by weight from 3.9
parts by weight in Example 26, the amount of red phosphorus used
was changed to 6.0 parts by weight from 3.8 parts by weight in
Example 26, the amount of TMCPP used was changed to 7.0 parts by
weight from 4.4 parts by weight in Example 26, and the amount of
HBB used was changed to 3.0 parts by weight from 1.9 parts by
weight in Example 26.
[0289] The results are shown in Table 3.
Example 28
[0290] The test was performed in exactly the same manner as in
Example 26, except that, compared to Example 26, the amount of the
foaming agent HFC used was changed to 4.6 parts by weight from 3.9
parts by weight in Example 26, the amount of red phosphorus used
was changed to 7.5 parts by weight from 3.8 parts by weight in
Example 26, the amount of TMCPP used was changed to 8.8 parts by
weight from 4.4 parts by weight in Example 26, and the amount of
HBB used was changed to 3.8 parts by weight from 1.9 parts by
weight in Example 26.
[0291] The results are shown in Table 3.
Example 29
[0292] The test was performed in exactly the same manner as in
Example 26, except that, compared to Example 26, the amount of the
foaming agent HFC used was changed to 6.1 parts by weight from 3.9
parts by weight in Example 26, the amount of red phosphorus used
was changed to 15.0 parts by weight from 3.8 parts by weight in
Example 26, the amount of TMCPP used was changed to 17.5 parts by
weight from 4.4 parts by weight in Example 26, and the amount of
HBB used was changed to 7.5 parts by weight from 1.9 parts by
weight in Example 26.
[0293] The results are shown in Table 3.
Example 30
[0294] The test was performed in exactly the same manner as in
Example 22, except that, compared to Example 22, the amount of the
foaming agent HFC used was changed to 4.3 parts by weight from 3.5
parts by weight in Example 22, the amount of red phosphorus used
was changed to 6.0 parts by weight from 5.0 parts by weight in
Example 22, the amount of ammonium dihydrogen phosphate used was
changed to 3.0 parts by weight from 2.5 parts by weight in Example
22, and 6.0 parts by weight of zinc borate was used instead of
HBB.
[0295] The results are shown in Table 3.
TABLE-US-00003 TABLE 3 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 21 ple 22 ple 23 ple 24 ple 25 ple 26 ple 27
ple 28 ple 29 ple 30 Polyol Polyol A-1 21.8 21.8 21.8 21.8 21.8
21.8 21.8 21.8 21.8 21.8 composition compound A-2 -- -- -- -- -- --
-- -- -- -- A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- --
-- -- -- -- A-5 -- -- -- -- -- -- -- -- -- -- A-6 -- -- -- -- -- --
-- -- -- -- A-7 -- -- -- -- -- -- -- -- -- -- A-8 -- -- -- -- -- --
-- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 stabiliser
Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 catalyst
B-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 catalyst Foaming agent Water 0.6
0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 HFC 6.4 3.5 3.9 4.5 5.5 3.9 4.4
4.6 6.1 4.3 Polyisocyanate 78.2 78.2 78.2 78.2 78.2 78.2 78.2 78.2
78.2 78.2 Additive Red C-1 15.0 5.0 6.0 10.0 20.0 3.8 6.0 7.5 15.0
6.0 phosphorus Ammonium C-2 7.5 2.5 3.0 5.0 10.0 -- -- -- -- 3.0
dihydrogen phosphate TMCPP C-3 17.5 -- -- -- -- 4.4 7.0 8.8 17.5 --
HBB C-4 -- 2.5 3.0 5.0 10.0 1.9 3.0 3.8 7.5 -- Zinc borate C-5 --
-- -- -- -- -- -- -- -- 6.0 Antimony C-6 -- -- -- -- -- -- -- -- --
-- trioxide Aluminum C-7 -- -- -- -- -- -- -- -- -- -- hydroxide
Density (g/cm.sup.3) 0.055 0.050 0.055 0.055 0.052 0.055 0.055
0.055 0.055 0.055 Isocyanate INDEX 400 400 400 400 400 400 400 400
400 400 Gross calorific value (MJ/m.sup.2): 7.4 5.3 4.6 3.8 7.1 7.3
4.1 4.1 6.8 6.4 after elapse of 10 minutes Gross calorific value
(MJ/m.sup.2): 9.9 7.5 5.4 5.2 10.9 9.2 5.3 5.6 10.8 9.3 after
elapse of 20 minutes Gross calorific value .largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle. .largecircle.
.largecircle..largecircle. .largecircle..largecircle. .largecircle.
.largecircle. State of Expansion .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. residue
Deformation .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Contraction .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
Determination OK OK OK OK OK OK OK OK OK OK
Example 31
[0296] The test was performed in exactly the same manner as in
Example 22, except that, compared to Example 22, the amount of the
foaming agent HFC used was changed to 4.4 parts by weight from 3.5
parts by weight in Example 22, the amount of red phosphorus used
was changed to 6.0 parts by weight from 5.0 parts by weight in
Example 22, 7.0 parts by weight of TMCPP was used instead of
ammonium dihydrogen phosphate, and 6.0 parts by weight of zinc
borate was used instead of EBB.
[0297] The results are shown in Table 4.
Example 32
[0298] The test was performed in exactly the same manner as in
Example 31, except that, compared to Example 31, the amount of the
foaming agent EEC used was changed to 4.2 parts by weight from 4.4
parts by weight in Example 31, and 3.0 parts by weight of EBB was
used instead of TMCPP.
[0299] The results are shown in Table 4.
Example 33
[0300] The test was performed in exactly the same manner as in
Example 18, except that, compared to Example 18, the amount of red
phosphorus used was changed to 3.2 parts by weight from 3.8 parts
by weight in Example 18, the amount of ammonium dihydrogen
phosphate used was changed to 1.6 parts by weight from 1.9 parts by
weight in Example 18, the amount of TMCPP used was changed to 3.6
parts by weight from 4.4 parts by weight in Example 18, and 1.6
parts by weight of HBB was used
[0301] The results are shown in Table 4.
Example 34
[0302] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
foaming agent HFC used was changed to 4.7 parts by weight from 3.9
parts by weight in Example 33, the amount of red phosphorus used
was changed to 6.0 parts by weight from 3.2 parts by weight in
Example 33, the amount of ammonium dihydrogen phosphate used was
changed to 3.0 parts by weight from 1.6 parts by weight in Example
33, the amount of TMCPP used was changed to 7.0 parts by weight
from 3.6 parts by weight in Example 33, and the amount of HER used
was changed to 3.0 parts by weight from 1.6 parts by weight in
Example 33.
[0303] The results are shown in Example 4.
Example 35
[0304] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
foaming agent HFC used was changed to 6.0 parts by weight from 3.9
parts by weight in Example 33, the amount of red phosphorus used
was changed to 9.5 parts by weight from 3.2 parts by weight in
Example 33, the amount of ammonium dihydrogen phosphate used was
changed to 4.7 parts by weight from 1.6 parts by weight in Example
33, the amount of TMCPP used was changed to 11.1 parts by weight
from 3.6 parts by weight in Example 33, and the amount of HBB used
was changed to 4.7 parts by weight from 1.6 parts by weight in
Example 33.
[0305] The results are shown in Example 4.
Example 36
[0306] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
foaming agent HFC used was changed to 6.4 parts by weight from 3.9
parts by weight in Example 33, the amount of red phosphorus used
was changed to 12.6 parts by weight from 3.2 parts by weight in
Example 33, the amount of ammonium dihydrogen phosphate used was
changed to 6.3 parts by weight from 1.6 parts by weight in Example
33, the amount of TMCPP used was changed to 14.8 parts by weight
from 3.6 parts by weight in Example 33, and the amount of EBB used
was changed to 6.3 parts by weight from 1.6 parts by weight in
Example 33.
[0307] The results are shown in Example 4.
Example 37
[0308] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
foaming agent HFC used was changed to 7.9 parts by weight from 3.9
parts by weight in Example 33, the amount of red phosphorus used
was changed to 15.0 parts by weight from 3.2 parts by weight in
Example 33, the amount of ammonium dihydrogen phosphate used was
changed to 7.9 parts by weight from 1.6 parts by weight in Example
33, the amount of TMCPP used was changed to 18.4 parts by weight
from 3.6 parts by weight in Example 33, and the amount of HBB used
was changed to 7.9 parts by weight from 1.6 parts by weight in
Example 33.
[0309] The results are shown in Example 4.
Example 38
[0310] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
foaming agent HFC used was changed to 4.7 parts by weight from 3.9
parts by weight in Example 33, the amount of red phosphorus used
was changed to 6.0 parts by weight from 3.2 parts by weight in
Example 33, the amount of ammonium dihydrogen phosphate used was
changed to 3.0 parts by weight from 1.6 parts by weight in Example
33, the amount of TMCPP used was changed to 7.0 parts by weight
from 3.6 parts by weight in Example 33, the amount of HBB used was
changed to 3.0 parts by weight from 1.6 parts by weight in Example
33, and 6.0 parts by weight of zinc borate was used.
[0311] The results are shown in Example 4.
Example 39
[0312] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of the
polyol compound A-1 used was changed to 35.8 parts by weight from
21.8 parts by weight in Example 34, the amount of polyisocyanate
used was changed to 64.2 parts by weight from 78.2 parts by weight
in Example 34, and the amount of the foaming agent HFC used was
changed to 4.6 parts by weight from 4.7 parts by weight in Example
34.
[0313] The results are shown in Table 4.
Example 40
[0314] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 27.1 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 72.9 parts by weight from 64.2
parts by weight in Example 39.
[0315] The results are shown in Table 4.
TABLE-US-00004 TABLE 4 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 31 ple 32 ple 33 ple 34 ple 35 ple 36 ple 37
ple 38 ple 39 ple 40 Polyol Polyol A-1 21.8 21.8 21.8 21.8 21.8
21.8 21.8 21.8 35.8 27.1 composition compound A-2 -- -- -- -- -- --
-- -- -- -- A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- --
-- -- -- -- A-5 -- -- -- -- -- -- -- -- -- -- A-6 -- -- -- -- -- --
-- -- -- -- A-7 -- -- -- -- -- -- -- -- -- -- A-8 -- -- -- -- -- --
-- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 stabilizer
Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 catalyst
B-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 catalyst Foaming agent Water 0.6
0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 HFC 4.4 4.2 3.9 4.7 6.0 6.4 7.9
4.7 4.6 4.6 Polyisocyanate 78.2 78.2 78.2 78.2 78.2 78.2 78.2 78.2
64.2 72.9 Additive Red C-1 6.0 6.0 3.2 6.0 9.5 12.6 15.8 6.0 6.0
6.0 phosphorus Ammonium C-2 -- -- 1.6 3.0 4.7 6.3 7.9 3.0 3.0 3.0
dihydrogen phosphate TMCPP C-3 7.0 -- 3.6 7.0 11.1 14.8 18.4 7.0
7.0 7.0 HBB C-4 -- 3.0 1.6 3.0 4.7 6.3 7.9 3.0 3.0 3.0 Zinc borate
C-5 6.0 6.0 -- -- -- -- -- 6.0 -- -- Antimony C-6 -- -- -- -- -- --
-- -- -- -- trioxide Aluminum C-7 -- -- -- -- -- -- -- -- -- --
hydroxide Density (g/cm.sup.3) 0.055 0.055 0.054 0.055 0.057 0.056
0.059 0.055 0.054 0.055 Isocyanate INDEX 400 400 400 400 400 400
400 400 200 300 Gross calorific value (MJ/m.sup.2): 4.0 3.7 3.7 2.0
3.2 3.9 5.6 5.1 3.8 4.3 after elapse of 10 minutes Gross calorific
value (MJ/m.sup.2): 5.0 5.4 7.0 4.2 6.6 7.6 7.7 6.1 5.5 5.3 after
elapse of 20 minutes Gross calorific value
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle. State of
Expansion .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. residue Deformation .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Contraction .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Determination OK OK OK OK
OK OK OK OK OK OK
Example 41
[0316] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 18.2 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 81.8 parts by weight from 64.2
parts by weight in Example 39.
[0317] The results are shown in Table 5.
Example 42
[0318] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 15.7 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 84.3 parts by weight from 64.2
parts by weight in Example 39.
[0319] The results are shown in Table 5.
Example 43
[0320] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 13.7 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 86.3 parts by weight from 64.2
parts by weight in Example 39.
[0321] The results are shown in Table 5.
Example 44
[0322] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 12.2 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 87.8 parts by weight from 64.2
parts by weight in Example 39.
[0323] The results are shown in Table 5.
Example 45
[0324] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 11.0 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 89.0 parts by weight from 64.2
parts by weight in Example 39.
[0325] The results are shown in Table 5.
Example 46
[0326] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 10.0 parts by weight from
35.8 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 90.0 parts by weight from 64.2
parts by weight in Example 39.
[0327] The results are shown in Table 5.
Example 47
[0328] The test was performed in exactly the same manner as in
Example 39, except that, compared to. Example 39, 16.6 parts by
weight of the polyol compound A-2 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
83.4 parts by weight from 64.2 parts by weight in Example 39.
[0329] The results are shown in Table 5.
Example 48
[0330] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, 21.4 parts by
weight of the polyol compound A-3 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
78.6 parts by weight from 64.2 parts by weight in Example 39.
[0331] The results are shown in Table 5.
Example 49
[0332] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, 27.6 parts by
weight of the polyol compound A-4 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
72.4 parts by weight from 64.2 parts by weight in Example 39.
[0333] The results are shown in Table 5.
Example 50
[0334] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, 21.8 parts by
weight of the polyol compound A-5 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
78.2 parts by weight from 64.2 parts by weight in Example 39.
[0335] The results are shown in Table 5.
TABLE-US-00005 TABLE 5 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 41 ple 42 ple 43 ple 44 ple 45 ple 46 ple 47
ple 48 ple 49 ple 50 Polyol Polyol A-1 18.2 15.7 13.7 12.2 11.0
10.0 -- -- -- -- composition compound A-2 -- -- -- -- -- -- 16.6 --
-- -- A-3 -- -- -- -- -- -- -- 21.4 -- -- A-4 -- -- -- -- -- -- --
-- 27.6 -- A-5 -- -- -- -- -- -- -- -- -- 21.8 A-6 -- -- -- -- --
-- -- -- -- -- A-7 -- -- -- -- -- -- -- -- -- -- A-8 -- -- -- -- --
-- -- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7
stabilizer Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
0.5 catalyst B-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7
Urethanization 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 catalyst
Foaming agent Water 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 HFC 4.6
4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 4.6 Polyisocyanate 81.8 84.3 86.3
87.8 89.0 90.0 83.4 78.6 72.4 78.2 Additive Red C-1 6.0 6.0 6.0 6.0
6.0 6.0 6.0 6.0 6.0 6.0 phosphorus Ammonium C-2 3.0 3.0 3.0 3.0 3.0
3.0 3.0 3.0 3.0 3.0 dihydrogen phosphate TMCPP C-3 7.0 7.0 7.0 7.0
7.0 7.0 7.0 7.0 7.0 7.0 HBB C-4 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
3.0 Zinc borate C-5 -- -- -- -- -- -- -- -- -- -- Antimony C-6 --
-- -- -- -- -- -- -- -- -- trioxide Aluminum C-7 -- -- -- -- -- --
-- -- -- -- hydroxide Density (g/cm.sup.3) 0.055 0.052 0.054 0.058
0.055 0.053 0.055 0.052 0.054 0.056 Isocyanate INDEX 500 600 700
800 900 1000 400 400 400 400 Gross calorific value (MJ/m.sup.2):
4.5 3.7 3.4 5.6 5.5 4.7 6.5 6.2 7.1 7.7 after elapse of 10 minutes
Gross calorific value (MJ/m.sup.2): 6.2 6.8 5.9 7.0 7.0 7.1 8.7 8.5
8.1 12.7 after elapse of 20 minutes Gross calorific value
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. State of Expansion
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. residue Deformation .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Contraction .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Determination OK OK OK OK
OK OK OK OK OK OK
Example 51
[0336] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, 16.6 parts by
weight of the polyol compound A-6 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
83.4 parts by weight from 64.2 parts by weight in Example 39.
[0337] The results are shown in Table 6.
Example 52
[0338] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, 15.3 parts by
weight of the polyol compound A-7 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
84.7 parts by weight from 64.2 parts by weight in Example 39.
[0339] The results are shown in Table 6.
Example 53
[0340] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, 16.7 parts by
weight of the polyol compound A-8 was used instead of the polyol
compound A-1, and the amount of polyisocyanate used was changed to
83.3 parts by weight from 64.2 parts by weight in Example 39.
[0341] The results are shown in Table 6.
Example 54
[0342] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 21.8 parts by weight from
35.8 parts by weight in Example 39, the amount of each of the
trimerization catalysts B-1 and B-2 used was changed to 1.3 parts
by weight and 1.7 parts by weight respectively from 0.5 parts by
weight and 0.7 parts by weight in Example 39, and the amount of
polyisocyanate used was changed to 78.2 parts by weight from 64.2
parts by weight in Example 39.
[0343] The results are shown in Table 6.
Example 55
[0344] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 21.8 parts by weight from
35.8 parts by weight in Example 39, 0.8 parts by weight of B-3 was
used instead of the trimerization catalysts B-1 and B-2, and the
amount of polyisocyanate used was changed to 78.2 parts by weight
from 64.2 parts by weight in Example 39.
[0345] The results are shown in Table 6.
Example 56
[0346] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 21.8 parts by weight from
35.8 parts by weight in Example 39, the amount of the trimerization
catalyst B-1 used was changed to 1.0 part by weight from 0.5 parts
by weight, B-2 was not used, and the amount of polyisocyanate used
was changed to 78.2 parts by weight from 64.2 parts by weight in
Example 39.
[0347] The results are shown in Table 6.
Example 57
[0348] The test was performed in exactly the same manner as in
Example 39, except that the amount of the polyol compound A-1 used
was changed to 29.5 parts by weight from 35.8 parts by weight in
Example 39, water was not used in the foaming agent, the amount of
HFC used was changed to 10.0 parts by weight from 4.6 parts by
weight, and the amount of polyisocyanate used was changed to 70.5
parts by weight from 64.2 parts by weight in Example 39.
[0349] The results are shown in Table 6.
Example 58
[0350] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 21.8 parts by weight from
35.8 parts by weight in Example 39, the amount of HFC used was
changed to 16.0 parts by weight from 4.6 parts by weight, and the
amount of polyisocyanate used was changed to 78.2 parts by weight
from 64.2 parts by weight in Example 39.
[0351] The results are shown in Table 6.
Example 59
[0352] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 21.8 parts by weight from
35.8 parts by weight in Example 39, HFC was not used, and the
amount of polyisocyanate used was changed to 78.2 parts by weight
from 64.2 parts by weight in Example 39.
[0353] The results are shown in Table 6.
Example 60
[0354] The test was performed in exactly the same manner as in
Example 39, except that, compared to Example 39, the amount of the
polyol compound A-1 used was changed to 24.8 parts by weight from
35.8 parts by weight in Example 39, the amount of water used in the
foaming agent was changed to 0.3 parts by weight from 0.6 parts by
weight, HFC was not used, and the amount of polyisocyanate used was
changed to 75.2 parts by weight from 64.2 parts by weight in
Example 39.
[0355] The results are shown in Table 6.
TABLE-US-00006 TABLE 6 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 51 ple 52 ple 53 ple 54 ple 55 ple 56 ple 57
ple 58 ple 59 ple 60 Polyol Polyol A-1 -- -- -- 21.8 21.8 21.8 29.5
21.8 21.8 24.8 composition compound A-2 -- -- -- -- -- -- -- -- --
-- A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- -- -- -- --
-- A-5 -- -- -- -- -- -- -- -- -- -- A-6 16.6 -- -- -- -- -- -- --
-- -- A-7 -- 15.3 -- -- -- -- -- -- -- -- A-8 -- -- 16.7 -- -- --
-- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 stabilizer
Trimerization B-1 0.5 0.5 0.5 1.3 -- 1.0 0.5 0.5 0.5 0.5 catalyst
B-2 0.7 0.7 0.7 1.7 -- -- 0.7 0.7 0.7 0.7 B-3 -- -- -- -- 0.8 -- --
-- -- -- Urethanization 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
catalyst Foaming agent Water 0.6 0.6 0.6 0.6 0.6 0.6 -- 0.6 0.6 0.3
HFC 4.6 4.6 4.6 4.6 4.6 4.6 10.0 16.0 -- -- Pentane -- -- -- -- --
-- -- -- -- -- Polyisocyanate 83.4 84.7 83.3 78.2 78.2 78.2 70.5
78.2 78.2 75.2 Additive Red C-1 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
6.0 phosphorus Ammonium C-2 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
dihydrogen phosphate TMCPP C-3 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0
7.0 HBB C-4 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Zinc borate C-5
-- -- -- -- -- -- -- -- -- -- Antimony C-6 -- -- -- -- -- -- -- --
-- -- trioxide Aluminum C-7 -- -- -- -- -- -- -- -- -- -- hydroxide
Density (g/cm.sup.3) 0.051 0.052 0.051 0.051 0.058 0.059 0.052
0.035 0.080 0.123 Isocyanate INDEX 400 400 400 400 400 400 400 400
400 400 Gross calorific value (MJ/m.sup.2): 7.3 6.9 7.3 4.2 3.8 4.4
2.3 4.4 5.3 5.3 after elapse of 10 minutes Gross calorific value
(MJ/m.sup.2): 9.2 9.5 10.1 5.7 4.8 6.1 4.9 6.5 7.1 8.5 after elapse
of 20 minutes Gross calorific value .largecircle. .largecircle.
.largecircle. .largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle. .largecircle.
State of Expansion .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. residue Deformation
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Contraction .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
Determination OK OK OK OK OK OK OK OK OK OK
Example 61
[0356] The test was performed in exactly the same manner as in
Example 6, except that, compared to Example 6, the amount of HFC
used was changed to 3.5 parts by weight from 3.7 parts by weight,
and 3.0 parts by weight of diammonium hydrogen phosphate was used
instead of TMCPP.
[0357] The results are shown in Table 7.
Example 62
[0358] The test was performed in exactly the same manner as in
Example 61, except that, compared to Example 61, 3.0 parts by
weight of aluminum phosphate monobasic was used instead of
diammonium hydrogen phosphate.
[0359] The results are shown in Table 7.
Example 63
[0360] The test was performed in exactly the same manner as in
Example 61, except that, compared to Example 61, 3.0 parts by
weight of sodium phosphate monobasic was used instead of diammonium
hydrogen phosphate.
[0361] The results are shown in Table 7.
Example 64
[0362] The test was performed in exactly the same manner as in
Example 61, except that, compared to Example 61, 3.0 parts by
weight of ammonium polyphosphate was used instead of diammonium
hydrogen phosphate.
[0363] The results are shown in Table 7.
Example 65
[0364] The test was performed in exactly the same manner as in
Example 61, except that, compared to Example 61, the amount of HFC
used was changed to 4.0 parts by weight from 3.5 parts by weight,
and 7.0 parts by weight of a phosphoric acid ester 1 was used
instead of diammonium hydrogen phosphate.
[0365] The results are shown in Table 7.
Example 66
[0366] The test was performed in exactly the same manner as in
Example 65, except that, compared to Example 65, 7.0 parts by
weight of a phosphoric acid ester 2 was used instead of the
phosphoric acid ester 1.
[0367] The results are shown in Table V.
Example 67
[0368] The test was performed in exactly the same manner as in
Example 61, except that, compared to Example 61, 3.0 parts by
weight of ammonium dihydrogen phosphate and 7.0 parts by weight of
TMCPP were used, and 3.0 parts by weight of EBTBPI was used instead
of diammonium hydrogen phosphate.
[0369] The results are shown in Example 7.
Example 68
[0370] The test was performed in exactly the same manner as in
Example 67, except that, compared to Example 67, 3.0 parts by
weight of EBTBP was used instead of EBTBPI.
[0371] The results are shown in Table 7.
Example 69
[0372] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
polyol compound A-1 used was changed to 15.8 parts by weight from
21.8 parts by weight in Example 33, the amount of polyisocyanate
used was changed to 84.2 parts by weight from 78.2 parts by weight
in Example 33, the amount of the foaming agent HFC used was changed
to 4.4 parts by weight from 3.9 parts by weight in Example 33, the
amount of red phosphorus used was changed to 3.8 parts by weight
from 3.2 parts by weight in Example 33, the amount of ammonium
dihydrogen phosphate used was changed to 1.9 parts by weight from
1.6 parts by weight in Example 33, the amount of TMCPP used was
changed to 4.4 parts by weight from 3.6 parts by weight in Example
33, and the amount of HBB used was changed to 1.9 parts by weight
from 1.6 parts by weight in Example 33.
[0373] The results are shown in Table 7.
Example 70
[0374] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
polyol compound A-1 used was changed to 17.7 parts by weight from
21.8 parts by weight in Example 39, the amount of polyisocyanate
used was changed to 82.3 parts by weight from 78.2 parts by weight
in Example 33, the amount of red phosphorus used was changed to 3.0
parts by weight from 3.2 parts by weight in Example 33, the amount
of ammonium dihydrogen phosphate used was changed to 1.5 parts by
weight from 1.6 parts by weight in Example 33, the amount of TMCPP
used was changed to 3.5 parts by weight from 3.6 parts by weight in
Example 33, and the amount of HBB used was changed to 1.5 parts by
weight from 1.6 parts by weight in Example 33.
[0375] The results are shown in Table 7.
TABLE-US-00007 TABLE 7 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple 61 ple 62 ple 63 ple 64 ple 65 ple 66 ple 67
ple 68 ple 69 ple 70 Polyol Polyol A-1 21.8 21.8 21.8 21.8 21.8
21.8 21.8 21.8 15.8 17.7 composition compound A-2 -- -- -- -- -- --
-- -- -- -- A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- --
-- -- -- -- A-5 -- -- -- -- -- -- -- -- -- -- A-6 -- -- -- -- -- --
-- -- -- -- A-7 -- -- -- -- -- -- -- -- -- -- A-8 -- -- -- -- -- --
-- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 stabilizer
Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 catalyst
B-2 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 catalyst Foaming agent Water 0.6
0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 HFC 3.5 3.5 3.5 3.5 4.0 4.0 4.7
4.7 4.4 3.9 Pentane -- -- -- -- -- -- -- -- -- -- Polyisocyanate
78.2 78.2 78.2 78.2 78.2 78.2 78.2 78.2 84.2 82.3 Additive Red C-1
6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 3.8 3.0 phosphorus Ammonium C-2 --
-- -- -- -- -- 3.0 3.0 1.9 1.5 dihydrogen phosphate TMCPP C-3 -- --
-- -- -- -- 7.0 7.0 4.4 3.5 HBB C-4 -- -- -- -- -- -- -- -- 1.9 1.5
Zinc borate C-5 -- -- -- -- -- -- -- -- -- -- Antimony C-6 -- -- --
-- -- -- -- -- -- trioxide Aluminum C-7 -- -- -- -- -- -- -- -- --
-- hydroxide Diammonium C-8 3.0 -- -- -- -- -- -- -- -- -- hydrogen
phosphate Aluminum C-9 -- 3.0 -- -- -- -- -- -- -- -- phosphate
monobasic Sodium C-10 -- -- 3.0 -- -- -- -- -- -- -- phosphate
monobasic Ammonium C-11 -- -- -- 3.0 -- -- -- -- -- --
polyphosphate Phosphoric C-12 -- -- -- -- 7.0 -- -- -- -- -- acid
ester 1 Phosphoric C-13 -- -- -- -- -- 7.0 -- -- -- -- acid ester 2
EBTBPI C-14 -- -- -- -- -- -- 3.0 -- -- -- EBTBP C-15 -- -- -- --
-- -- -- 3.0 -- -- Density (g/cm.sup.3) 0.052 0.054 0.051 0.054
0.055 0.057 0.054 0.055 0.058 0.056 Isocyanate INDEX 400 400 400
400 400 400 400 400 590 520 Gross calorific value (MJ/m.sup.2): 2.3
2.1 4.7 3.0 4.0 3.9 4.2 3.9 3.0 3.9 after elapse of 10 minutes
Gross calorific value (MJ/m.sup.2): 4.4 4.4 6.6 5.5 4.9 5.0 5.6 5.9
4.3 6.0 after elapse of 20 minutes Gross calorific value
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. .largecircle..largecircle. State of
Expansion .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. residue Deformation .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Contraction .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Determination OK OK OK OK
OK OK OK OK OK OK
Example 71
[0376] The test was performed in exactly the same manner as in
Example 33, except that, compared to Example 33, the amount of the
polyol compound A-1 used was changed to 16.8 parts by weight from
21.8 parts by weight in Example 33, the amount of polyisocyanate
used was changed to 83.2 parts by weight from 78.2 parts by weight
in Example 33, the amount of HFC used was changed to 6.0 parts by
weight from 3.9 parts by weight, the amount of red phosphorus used
was changed to 9.6 parts by weight from 3.2 parts by weight in
Example 33, the amount of ammonium dihydrogen phosphate used was
changed to 4.8 parts by weight from 1.6 parts by weight in Example
33, the amount of TMCPP used was changed to 11.2 parts by weight
from 3.6 parts by weight in Example 33, and the amount of HBB used
was changed to 4.8 parts by weight from 1.6 parts by weight in
Example 33.
[0377] The results are shown in Table 8.
Example 72
[0378] The test was performed in exactly the same manner as in
Example 71, except that, compared to Example 71, the amount of the
polyol compound A-1 used was changed to 30.6 parts by weight from
16.8 parts by weight in Example 71, and the amount of
polyisocyanate used was changed to 69.4 parts by weight from 83.2
parts by weight in Example 71.
[0379] The results are shown in Table 8.
Example 73
[0380] The test was performed in exactly the same manner as in
Example 71, except that, compared to Example 71, the amount of the
polyol compound A-1 used was changed to 26.4 parts by weight from
16.8 parts by weight in Example 71, the amount of HFC used was
changed to 6.4 parts by weight from 6.0 parts by weight, the amount
of polyisocyanate used was changed to 70.6 parts by weight from
83.2 parts by weight in Example 71, the amount of red phosphorus
used was changed to 13.3 parts by weight from 9.6 parts by weight
in Example 71, the amount of ammonium dihydrogen phosphate was
changed to 6.6 parts by weight from 4.8 parts by weight in Example
71, the amount of TMCPP used was changed to 15.5 parts by weight
from 11.2 parts by weight in Example 71, and the amount of HBB used
was changed to 6.6 parts by weight from 4.8 parts by weight in
Example 71.
[0381] The results are shown in Table 8.
Example 74
[0382] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of the
foam stabilizer used was changed to 6.8 parts by weight from 1.7
parts by weight in Example 34.
[0383] The results are shown in Table 8.
Example 75
[0384] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of the
foam stabilizer used was changed to 10.0 parts by weight from 1.7
parts by weight in Example 34.
[0385] The results are shown in Table 8.
Example 76
[0386] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the urethanization
catalyst was not used.
[0387] The results are shown in Table 8.
TABLE-US-00008 TABLE 8 Example Example Example Example Example
Example 71 72 73 74 75 76 Polyol Polyol A-1 16.8 30.6 26.4 21.8
21.8 21.8 composition compound A-2 -- -- -- -- -- -- A-3 -- -- --
-- -- -- A-4 -- -- -- -- -- -- A-5 -- -- -- -- -- -- A-6 -- -- --
-- -- -- A-7 -- -- -- -- -- -- A-8 -- -- -- -- -- -- Foam 1.7 1.7
1.7 6.8 10.0 1.7 stabilizer Trimerization B-1 0.5 0.5 0.5 0.5 0.5
0.5 catalyst B-2 0.7 0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1 0.1
0.1 0.1 -- catalyst Foaming agent Water 0.6 0.6 0.6 0.6 0.6 0.6 HFC
6.0 6.0 6.4 4.7 4.7 4.7 Pentane -- -- -- -- -- -- Polyisocyanate
83.2 69.4 70.6 78.2 78.2 78.2 Additive Red C-1 9.6 9.6 13.3 6.0 6.0
6.0 phosphorus Ammonium C-2 4.8 4.8 6.6 3.0 3.0 3.0 dihydrogen
phosphate TMCPP C-3 11.2 11.2 15.5 7.0 7.0 7.0 HBB C-4 4.8 4.8 6.6
3.0 3.0 3.0 Zinc borate C-5 -- -- -- -- -- -- Antimony C-6 -- -- --
-- -- -- trioxide Aluminum C-7 -- -- -- -- -- -- hydroxide
Diammonium C-8 -- -- -- -- -- -- hydrogen phosphate Aluminum C-9 --
-- -- -- -- -- phosphate monobasic Sodium C-10 -- -- -- -- -- --
phosphate monobasic Ammonium C-11 -- -- -- -- -- -- polyphosphate
Phosphoric C-12 -- -- -- -- -- -- acid ester 1 Phosphoric C-13 --
-- -- -- -- -- acid ester 2 EBTBPI C-14 -- -- -- -- -- -- EBTBP
C-15 -- -- -- -- -- -- Density (g/cm.sup.3) 0.058 0.056 0.058 0.053
0.057 0.054 Isocyanate INDEX 550 250 270 400 400 400 Gross
calorific value (MJ/m.sup.2): 3.6 2.5 5.1 4.0 3.7 5.2 after elapse
of 10 minutes Gross calorific value (MJ/m.sup.2): 4.5 5.3 8.3 5.7
5.6 6.5 after elapse of 20 minutes Gross calorific value
.largecircle..largecircle. .largecircle..largecircle. .largecircle.
.largecircle..largecircle. .largecircle..largecircle.
.largecircle..largecircle. State of Expansion .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. residue Deformation .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. Contraction
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Determination OK OK OK OK OK OK
Comparative example 1
[0388] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of the
polyol compound A-1 used was changed to 52.7 parts by weight from
21.8 parts by weight in Example 1, the trimerization catalyst was
not used, the amount of HFC used was changed to 6.4 parts by weight
from 3.9 parts by weight, the amount of polyisocyanate used was
changed to 47.3 parts by weight from 78.2 parts by weight in
Example 1, and the additive was not used.
[0389] The results are shown in Table 9.
Comparative example 2
[0390] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of HFC
used was changed to 3.2 parts by weight from 3.9 parts by weight,
and the additive was not used.
[0391] The results are shown in Table 9.
Comparative example 3
[0392] The test was performed in exactly the same manner as in
Comparative example 2, except that, compared to Comparative example
2, the amount of HFC used was changed to 3.3 parts by weight from
3.2 parts by weight, and 3.0 parts by weight of red phosphorus was
used.
[0393] The results are shown in Table 9.
Comparative example 4
[0394] The test was performed in exactly the same manner as in
Comparative example 2, except that, compared to Comparative example
2, the amount of HFC used was changed to 3.4 parts by weight from
3.2 parts by weight, and 6.0 parts by weight of red phosphorus was
used.
[0395] The results are shown in Table 9.
Comparative example 5
[0396] The test was performed in exactly the same manner as in
Comparative example 2, except that, compared to Comparative example
2, the amount of HFC used was changed to 4.0 parts by weight from
3.2 parts by weight, and 12.0 parts by weight of red phosphorus was
used.
[0397] The results are shown in Table 9.
Comparative example 6
[0398] The test was performed in exactly the same manner as in
Comparative example 2, except that, compared to Comparative example
2, the amount of HFC used was changed to 4.8 parts by weight from
3.2 parts by weight, and 24.0 parts by weight of red phosphorus was
used.
[0399] The results are shown in Table 9.
Comparative example 7
[0400] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of the
polyol compound A-1 used was changed to 25.0 parts by weight from
21.8 parts by weight in Example 34, the foaming agent was not used,
the amount of HFC used was changed to 6.4 parts by weight from 4.7
parts by weight, and the amount of polyisocyanate used was changed
to 75.0 parts by weight from 78.2 parts by weight in Example
34.
[0401] The results are shown in Table 9.
Comparative example 8
[0402] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of HFC
used was changed to 4.4 parts by weight from 4.7 parts by weight,
and red phosphorus was not used.
[0403] The results are shown in Table 9.
Comparative example 9
[0404] The test was performed in exactly the same manner as in
Comparative example 8, except that, compared to Comparative example
8, the amount of HFC used was changed to 4.5 parts by weight from
4.4 parts by weight, and 6.0 parts by weight of zinc borate was
used instead of HBB.
[0405] The results are shown in Table 9.
Comparative example 10
[0406] The test was performed in exactly the same manner as in
Comparative example 8, except that, compared to Comparative example
8, the amount of HFC used was changed to 4.3 parts by weight from
4.4 parts by weight, and 6.0 parts by weight of zinc borate was
used instead of TMCPP.
[0407] The results are shown in Table 9.
TABLE-US-00009 TABLE 9 Compar- Compar- Compar- Compar- Compar-
Compar- Compa- Compar- Compar- Compar- ative ative ative ative
ative ative rative ative ative ative example example example
example example example example example example example 1 2 3 4 5 6
7 8 9 10 Polyol Polyol A-1 52.7 21.8 21.8 21.8 21.8 21.8 25.0 21.8
21.8 21.8 composi- compound A-2 -- -- -- -- -- -- -- -- -- -- tion
A-3 -- -- -- -- -- -- -- -- -- -- A-4 -- -- -- -- -- -- -- -- -- --
A-5 -- -- -- -- -- -- -- -- -- -- A-6 -- -- -- -- -- -- -- -- -- --
A-7 -- -- -- -- -- -- -- -- -- -- Foam 1.7 1.7 1.7 1.7 1.7 1.7 1.7
1.7 1.7 1.7 stabilizer Trimeriza- B-1 -- 0.5 0.5 0.5 0.5 0.5 0.5
0.5 0.5 0.5 tion catalyst B-2 -- 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7
0.7 Urethan- 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ization
catalyst Foaming Water 0.6 0.6 0.6 0.6 0.6 0.6 -- 0.6 0.6 0.6 agent
HFC 6.4 3.2 3.3 3.4 4.0 4.8 -- 4.4 4.5 4.3 Polyisocyanate 47.3 78.2
78.2 78.2 78.2 78.2 75.0 78.2 78.2 78.2 Additive Red C-1 -- -- 3.0
6.0 12.0 24.0 6.0 -- -- -- phospho- rus Ammo- C-2 -- -- -- -- -- --
3.0 3.0 3.0 3.0 nium dihydro- gen phos- phate TMCPP C-3 -- -- -- --
-- -- 7.0 7.0 7.0 HBB C-4 -- -- -- -- -- -- 3.0 3.0 -- 3.0 Zinc C-5
-- -- -- -- -- -- -- -- 6.0 6.0 borate Antimony C-6 -- -- -- -- --
-- -- -- -- -- trioxide Aluminum C-7 -- -- -- -- -- -- -- -- ~ --
hydroxide Density (g/cm.sup.3) 0.060 0.058 0.056 0.053 0.057 0.056
0.314 0.055 0.053 0.052 Isocyanate INDEX 100 400 400 400 400 400
400 400 400 400 Gross calorific value (MJ/m.sup.2): 34.9 32.5 10.2
8.3 9.1 17.3 25.9 9.6 13.9 20.1 after elapse of 10 minutes Gross
calorific value (MJ/m.sup.2): 51.8 51.2 16.4 11.6 12.3 26.5 34.0
13.5 15.9 26.0 after elapse of 20 minutes Gross calorific value X X
X X X X X X X X State of Expansion X .largecircle. .largecircle.
.largecircle. X .largecircle. .largecircle. X .largecircle.
.largecircle. residue Deformation X X .largecircle. .largecircle.
.largecircle. X X X X X Contraction X X X X X X .largecircle.
.largecircle. .largecircle. .largecircle. Determination NG NG NG NG
NG NG NG NG NG NG
Comparative example 11
[0408] The test was performed in exactly the same manner as in
Comparative example 9, except that, compared to Comparative example
9, 3.0 parts by weight of HBB was used instead of ammonium
dihydrogen phosphate.
[0409] The results are shown in Table 10.
Comparative example 12
[0410] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of HFC
used was changed to 3.7 parts by weight from 3.9 parts by weight,
the amount of red phosphorus used was changed to 2.0 parts by
weight from 3.0 parts by weight, and the amount of ammonium
dihydrogen phosphate was changed to 1.0 parts by weight from 9.0
parts by weight.
[0411] The results are shown in Table 10.
Comparative example 13
[0412] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of HFC
used was changed to 5.8 parts by weight from 3.9 parts by weight,
the amount of red phosphorus used was changed to 24.0 parts by
weight from 3.0 parts by weight, and the amount of ammonium
dihydrogen phosphate was changed to 12.0 parts by weight from 9.0
parts by weight.
[0413] The results are shown in Table 10.
Comparative example 14
[0414] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of HFC
used was changed to 4.6 parts by weight from 3.9 parts by weight,
the amount of red phosphorus used was changed to 2.3 parts by
weight from 3.0 parts by weight, and ammonium dihydrogen phosphate
was replaced with 2.7 parts by weight of TMCPP.
[0415] The results are shown in Table 10.
Comparative example 15
[0416] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of HFC
used was changed to 5.8 parts by weight from 3.9 parts by weight,
the amount of red phosphorus used was changed to 18.5 parts by
weight from 3.0 parts by weight, and ammonium dihydrogen phosphate
was replaced with 21.5 parts by weight of TMCPP.
[0417] The results are shown in Table 10.
Comparative example 16
[0418] The test was performed in exactly the same manner as in
Example 1, except that, compared to Example 1, the amount of HFC
used was changed to 5.8 parts by weight from 3.9 parts by weight,
the amount of red phosphorus used was changed to 26.7 parts by
weight from 3.0 parts by weight, and ammonium dihydrogen phosphate
was replaced with 13.3 parts by weight of EBB.
[0419] The results are shown in Table 10.
Comparative example 17
[0420] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of HFC
used was changed to 3.4 parts by weight from 4.7 parts by weight,
the amount of red phosphorus used was changed to 1.6 parts by
weight from 6.0 parts by weight, the amount of ammonium dihydrogen
phosphate used was changed to 0.8 parts by weight from 3.0 parts by
weight, the amount of TMCPP used was changed to 1.8 parts by weight
from 7.0 parts by weight, and the amount of HBB used was changed to
0.8 parts by weight from 3.0 parts by weight.
[0421] The results are shown in Table 10.
Comparative example 18
[0422] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of the
polyol compound A-1 used was changed to 52.7 parts by weight from
21.8 parts by weight in Example 34, the amount of HFC used was
changed to 4.6 parts by weight from 4.7 parts by weight, and the
amount of polyisocyanate used was changed to 47.3 parts by weight
from 78.2 parts by weight in Example 34.
[0423] The results are shown in Table 10.
Comparative example 19
[0424] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of each
of the trimerization catalysts B-1 and B-2 was changed to 0 parts
by weight and 0.1 parts by weight respectively from 0.5 parts by
weight and 0.7 parts by weight, and the amount of HFC used was
changed to 4.6 parts by weight from 4.7 parts by weight.
[0425] The results are shown in Table 10.
Comparative example 20
[0426] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of each
of the trimerization catalysts B-1 and B-2 was changed to 0.3 parts
by weight and 0 parts by weight respectively from 0.5 parts by
weight and 0.7 parts by weight, and the amount of HFC used was
changed to 4.6 parts by weight from 4.7 parts by weight.
[0427] The results are shown in Table 10.
Comparative example 21
[0428] The test was performed in exactly the same manner as in
Example 34, except that, compared to Example 34, the amount of each
of the trimerization catalysts B-1 and B-2 was changed to 0.2 parts
by weight and 0.3 parts by weight respectively from 0.5 parts by
weight and 0.7 parts by weight, and the amount of HFC used was
changed to 4.6 parts by weight from 4.7 parts by weight.
[0429] The results are shown in Table 10.
TABLE-US-00010 TABLE 10 Comparative Comparative Comparative
Comparative Comparative Comparative example example example example
example example 11 12 13 14 15 16 Polyol Polyol A-1 21.8 21.8 21.8
21.8 21.8 21.8 composition compound A-2 -- -- -- -- -- -- A-3 -- --
-- -- -- -- A-4 -- -- -- -- -- -- A-5 -- -- -- -- -- -- A-6 -- --
-- -- -- -- A-7 -- -- -- -- -- -- Foam stabilizer 1.7 1.7 1.7 1.7
1.7 1.7 Trimerization B-1 0.5 0.5 0.5 0.5 0.5 0.5 catalyst B-2 0.7
0.7 0.7 0.7 0.7 0.7 Urethanization 0.1 0.1 0.1 0.1 0.1 0.1 catalyst
Foaming agent Water 0.6 0.6 0.6 0.6 0.6 0.6 HFC 4.5 3.7 5.8 4.6 5.8
5.8 Polyisocyanate 78.2 78.2 78.2 78.2 78.2 78.2 Additive Red
phosphorus C-1 -- 2.0 24.0 2.3 18.5 26.7 Ammonium C-2 -- 1.0 12.0
-- -- -- dihydrogen phosphate TMCPP C-3 7.0 -- -- 2.7 21.5 -- HBB
C-4 3.0 -- -- -- -- 13.3 Zinc borate C-5 6.0 -- -- -- -- --
Antimony C-6 -- -- -- -- -- -- trioxide Aluminum C-7 -- -- -- -- --
-- hydroxide Density (g/cm.sup.3) 0.056 0.051 0.057 0.055 0.055
0.057 Isocyanate INDEX 400 400 400 400 400 400 Gross calorific
value (MJ/m.sup.2): 11.7 12.1 18.9 10.5 13.6 11.3 after elapse of
10 minutes Gross calorific value (MJ/m.sup.2): 18.6 15.0 23.8 13.9
17.6 15.2 after elapse of 20 minutes Gross calorific value X X X X
X X State of Expansion .largecircle. .largecircle. .largecircle. X
.largecircle. X residue Deformation X X X X X X Contraction
.largecircle. X .largecircle. .largecircle. .largecircle.
.largecircle. Determination NG NG NG NG NG NG Comparative
Comparative Comparative Comparative Comparative example example
example example example 17 18 19 20 21 Polyol Polyol A-1 21.8 52.7
21.8 21.8 21.8 composition compound A-2 -- -- -- -- -- A-3 -- -- --
-- -- A-4 -- -- -- -- -- A-5 -- -- -- -- -- A-6 -- -- -- -- -- A-7
-- -- -- -- -- Foam stabilizer 1.7 1.7 1.7 1.7 1.7 Trimerization
B-1 0.5 0.5 0.0 0.3 0.2 catalyst B-2 0.7 0.7 0.1 0.0 0.3
Urethanization 0.1 0.1 0.1 0.1 0.1 catalyst Foaming agent Water 0.6
0.6 0.6 0.6 0.6 HFC 3.4 4.6 4.6 4.6 4.6 Polyisocyanate 78.2 47.3
78.2 78.2 78.2 Additive Red phosphorus C-1 1.6 6.0 6.0 6.0 6.0
Ammonium C-2 0.8 3.0 3.0 3.0 3.0 dihydrogen phosphate TMCPP C-3 1.8
7.0 7.0 7.0 7.0 HBB C-4 0.8 3.0 3.0 3.0 3.0 Zinc borate C-5 -- --
-- -- -- Antimony C-6 -- -- -- -- -- trioxide Aluminum C-7 -- -- --
-- -- hydroxide Density (g/cm.sup.3) 0.052 0.053 Unfoamable
Unfoamable 0.053 Isocyanate INDEX 400 100 400 400 400 Gross
calorific value (MJ/m.sup.2): 12.0 8.1 -- -- 14.1 after elapse of
10 minutes Gross calorific value (MJ/m.sup.2): 15.6 10.8 -- -- 17.9
after elapse of 20 minutes Gross calorific value X X -- -- X State
of Expansion X X -- -- X residue Deformation X .largecircle. -- --
.largecircle. Contraction .largecircle. .largecircle. -- -- X
Determination NG NG -- -- NG
[0430] The molded article obtained from the flame-retardant
urethane resin composition according to one or more embodiments of
the present disclosure yields a small calorific value when it
combusts, and the residue thereof remaining after combustion
maintains a constant shape. Therefore, the molded article can
exhibit excellent fireproof properties.
[0431] Because the molded article formed of the flame-retardant
urethane resin composition according to one or more embodiments of
the present disclosure has excellent fireproof properties, the
flame-retardant urethane resin composition of one or more
embodiments of the present disclosure can be widely applied to
buildings and the like.
[0432] Although embodiments of the disclosure have been described
using specific terms, devices, and methods, such description is for
illustrative purposes only. The words used are words of description
rather than limitation. It is to be understood that changes and
variations may be made by those of ordinary skill in the art
without departing from the spirit or the scope of the present
disclosure, which is set forth in the following claims. In
addition, it should be understood that aspects of the various
embodiments may be interchanged in whole or in part. Therefore, the
spirit and scope of the appended claims should not be limited to
the description of the preferred versions contained therein.
* * * * *